CN109647534A - A kind of preparation method of NiB/PANI nano-fiber catalyst and its application in preparing hydrogen by sodium borohydride hydrolysis - Google Patents
A kind of preparation method of NiB/PANI nano-fiber catalyst and its application in preparing hydrogen by sodium borohydride hydrolysis Download PDFInfo
- Publication number
- CN109647534A CN109647534A CN201811546056.1A CN201811546056A CN109647534A CN 109647534 A CN109647534 A CN 109647534A CN 201811546056 A CN201811546056 A CN 201811546056A CN 109647534 A CN109647534 A CN 109647534A
- Authority
- CN
- China
- Prior art keywords
- nib
- nano
- pani
- fiber
- polystyrene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002121 nanofiber Substances 0.000 title claims abstract description 71
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 63
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000001257 hydrogen Substances 0.000 title claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 30
- 229910000033 sodium borohydride Inorganic materials 0.000 title claims abstract description 27
- 239000012279 sodium borohydride Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 8
- 239000004793 Polystyrene Substances 0.000 claims abstract description 79
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 56
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000243 solution Substances 0.000 claims abstract description 45
- 239000002071 nanotube Substances 0.000 claims abstract description 30
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920002223 polystyrene Polymers 0.000 claims abstract description 26
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000002131 composite material Substances 0.000 claims abstract description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 230000009467 reduction Effects 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000001291 vacuum drying Methods 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 10
- 238000006277 sulfonation reaction Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 238000001523 electrospinning Methods 0.000 claims description 2
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 238000000967 suction filtration Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 238000003860 storage Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 150000001768 cations Chemical class 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002114 nanocomposite Substances 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 238000002525 ultrasonication Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 3
- 239000002322 conducting polymer Substances 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910020674 Co—B Inorganic materials 0.000 description 1
- 229910003252 NaBO2 Inorganic materials 0.000 description 1
- 241000255964 Pieridae Species 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 101150035024 lgt1 gene Proteins 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000007787 solid 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
-
- 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 invention belongs to synthesize composite catalyst field, in particular to the preparation method of a kind of NiB/PANI nano-fiber catalyst and its application in preparing hydrogen by sodium borohydride hydrolysis, include the following steps: that (1) takes polystyrene to be dissolved in n,N-Dimethylformamide, is made into electrostatic spinning precursor solution A；(2) polystyrene nano fiber B is made；(3) nanofiber B is immersed in the concentrated sulfuric acid, obtains sulfonated polystyrene nanometer, is then rinsed and be dried to obtain nanofiber C；(4) nanofiber C is soaked in aniline solution, ammonium persulfate reaction is added, obtains composite nano fiber D；(5) composite nano fiber D is soaked in tetrahydrofuran and obtains nanotube E；(6) nanotube E is immersed in nickel source aqueous solution, reduction nickel source is NiB to get target product.Low in investment cost of the present invention, specific surface area of catalyst is big, good dispersion, and stability is high, can be repeated several times use, and be easily recycled.
Description
Technical field
It is the invention belongs to synthesize composite catalyst field, in particular to a kind of with the nano tube supported amorphous alloy of PANI
NiB(NiB/PANI) preparation method of catalyst and its application in preparing hydrogen by sodium borohydride hydrolysis.
Background technique
In recent years, being continuously increased with energy demand, Hydrogen Energy is as exploitation and using by the extensive pass of people
Note.The hydrogen storage technology for how obtaining more highly effective and safe improves the specific energy of hydrogen as a bottleneck problem urgently to be resolved.
Current hydrogen storage technology has physics hydrogen storage and chemical hydrogen storage two major classes, and physics hydrogen storage technology includes high-pressure hydrogen storing, low-temperature liquefaction storage
Hydrogen and adsorption hydrogen-storing, chemical hydrogen storage include hydride hydrogen-storing, liquid organic hydrides hydrogen storage and inorganic matter hydrogen storage etc., but
These hydrogen storage technologies have some defects of itself, and for example equipment cost is high, and energy density is low, recyclability energy difference etc., now
It can't be applied in commercialized mobile or portable fuel battery.In recent years, NaBH4Hydrolytic hydrogen production is as a kind of
Concern of the new hydrogen production technology by numerous scientific research personnel conveniently, safely, this is because during preparing hydrogen by sodium borohydride hydrolysis
Not discharge of noxious gases, and hydrogen purity is high, the pernicious gas without containing fuel cell poisoning, simultaneously because not needing outer
Add energy, energy utilization efficiency is high, and hydrogen-storage density is up to 10.8wt%.Under room temperature, NaBH4Reacting with water can release
H2, chemical equation is as follows:
NaBH4+2H2O=4H2+NaBO2 (1)
The stability of the reaction is decided by NaBH4The temperature and pH value of aqueous solution, reaction rate follow public in following experience
Formula:
lgt1/2=pH-(0.34-1.72) (2)
From formula (2) it is recognised that under strongly alkaline conditions, the reaction rate is very slow, therefore in NaBH4Strong base solution in
Sodium borohydride can be stabilized.Utilize NaBH4Alkaline solution must have efficient hydrolyst to promote NaBH as hydrogen source4
Hydrogen is discharged rapidly out under running conditions.The NaBH currently developed4Hydrolyst is broadly divided into two classes: noble metal catalyst
And non-precious metal catalyst.Catalytic activity is very high for noble metal catalyst (such as metal Rh and Pt), but higher cost, it is difficult to big rule
Mould utilizes.Non-precious metal catalyst such as Fe-B, Co-B, Ni-B and Cu-B etc. have catalytic activity, wherein Ni base catalyst valence
Lattice are cheap, and catalytic activity is moderate, but ultrafine NiB amorphous alloy easily causes to roll into a ball since its particle is small and has magnetism
It is poly-.Being prepared into loaded catalyst with carrier of non-crystal NiB alloy to solve this problem becomes a kind of new approach.Field
Red scape etc. is the study found that using attapulgite clay as catalyst carrier, the catalysis that can significantly improve nickel-base catalyst is stablized
Property.Li Fang et al. opening immobilized CoB in carbon nanotube center, can make magnetic nanoparticle be fixed on carbon nanotube well
Inside, the catalyst have good catalytic activity in preparing hydrogen by sodium borohydride hydrolysis.These above-mentioned methods are all based on carrier
With seek to break through on solid support method, although some catalyst have preferable catalytic effect, prepared catalyst is immobilized strong
It spends low, it is poor to recycle effect.
Summary of the invention
The present invention is directed to provide a kind of process simplification in place of overcome the deficiencies in the prior art, equipment is reduced, cost of investment
Cheap, specific surface area of catalyst is big, good dispersion, and stability is high, the NiB/PANI that can be repeated several times use, and be easily recycled
The preparation method of nano-fiber catalyst.
The present invention also provides a kind of application of NiB/PANI nano-fiber catalyst in terms of Hydrogen production from sodium borohydride.
In order to solve the above technical problems, the present invention is implemented as follows:
A kind of preparation method of NiB/PANI nano-fiber catalyst, includes the following steps:
(1) using polystyrene and n,N-Dimethylformamide as raw material, polystyrene is taken to be dissolved in n,N-Dimethylformamide,
It is made into electrostatic spinning precursor solution A；
(2) precursor solution A obtained by step (1) is placed in syringe, polystyrene nano fiber B is made in electrostatic spinning；
(3) nanofiber B obtained by step (2) is immersed in the concentrated sulfuric acid, carries out sulfonation processing, is received to obtain sulfonated polystyrene
Rice, then it is rinsed well to be placed in baking oven be dried to obtain nanofiber C with deionized water；
(4) nanofiber C obtained by step (3) is soaked in aniline solution, ammonium persulfate is then added and reacts at low temperature, obtains
To composite nano fiber D；
(5) composite nano fiber D obtained by step (4) is soaked in removal polystyrene kernel in tetrahydrofuran and obtains nanotube E；
(6) nanotube E obtained by step (5) is immersed in nickel source aqueous solution, is then NiB with sodium borohydride reduction nickel source, i.e.,
Obtain target product NiB/PANI nano-tube composite catalyst.
As a preferred embodiment, nickel source is Nickel dichloride hexahydrate (II) in step (6) of the present invention.
Further, in the step (1) of the present invention, the mass ratio of n,N-Dimethylformamide and polystyrene is
100:10~20.
Further, in step (3) of the present invention, 40oC carries out sulfonation processing and receives to obtain sulfonated polystyrene
Rice.
Further, in step (4) of the present invention, the low temperature lower reaction time is for 24 hours；The ammonium persulfate and ammonium sulfate
Mass ratio be 1:1.
Further, in step (2) of the present invention, electrospinning conditions: voltage 18kV；Receiver drum rotation speed is
2000r/min；Receiving distance is 15cm；Polystyrene nano fiber B obtained is put into vacuum drying oven 2~3 hours.
Further, the present invention immerses nanofiber B obtained by step (2) in the concentrated sulfuric acid 4 hours, 40 DEG C of progress sulphurs of constant temperature
Change reaction.
Further, in step (4) of the present invention, nanofiber C obtained by step (3) is soaked in aniline solution,
Soaking time is 12 hours or more.
Further, in step (4) of the present invention, ammonium persulfate is added and is reacted 24 hours under 0~5 DEG C of environment, obtains
To composite nano fiber D.
Application of the above-mentioned NiB/PANI nano-fiber catalyst in preparing hydrogen by sodium borohydride hydrolysis.
PANI is a kind of conducting polymer organic compound, with excellent electric conductivity, is readily synthesized and stability
Well.By PS, it is dissolved in DMF solution then in high-voltage electrostatic spinning during system by nanofiber, then with PS nanofiber
PANI is formed in PS surface aggregate by raw material of aniline for template, finally removes PS kernel to obtain PANI nanotube.Institute
Preparing nanometer pipe outside diameter is about 200nm, and internal diameter is about 100nm.NaBH4Amorphous alloy catalyst NiB used in hydrolytic hydrogen production is
A kind of magnetic material easily reunited, this property results in poor dispersion of the catalyst in catalysis reaction, to reduce
The reaction rate of catalysis reaction.The surface and inside that NiB is loaded to PANI nanotube, considerably increase catalyst specific surface
Product, to improve the reaction rate of catalysis reaction.In addition, PANI nanotube has good electronics coupled to NiB amorphous particle
With steric hindrance protective effect, and effectively by-product deposition can be inhibited to adsorb.Therefore, the nano tube supported type catalysis of NiB/PANI
Agent is as NaBH4The catalyst of hydrogen manufacturing has good superiority.
The advantage of the invention is that conducting polymer medium PANI is to NiB's in the nano tube supported type catalyst of NiB/PANI
Stably dispersing acts on and effectively improves specific surface area of catalyst, and catalyst preparation process is easy to operate quickly, can be in normal temperature and pressure
Lower progress.
It is used to prepare the low in raw material price of NiB/PANI nano-tube composite catalyst in the present invention, overcomes noble metal and urges
The expensive price of agent, while recycling rate of waterused is improved, greatly reduce preparation cost.
The present invention is based on conducting polymer flexible nano tube materials as catalyst carrier, is remarkably improved point of catalyst
Performance is dissipated, catalyst is more stable to can be repeated several times use, and is easily recycled.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and specific embodiments.Protection scope of the present invention not only office
It is limited to the statement of following content.
Fig. 1 is PS Electrospun nano-fibers SEM of the present invention figure.
Fig. 2 is PANI nanotube TEM of the present invention figure.
Fig. 3 is the nano tube supported type catalyst TEM figure of NiB/PANI of the present invention.
Specific embodiment
Embodiment 1
With PS(polystyrene) and DMF(N, dinethylformamide) it is raw material, configuration concentration is that 10.0 wt% PS-DMF are molten
It is molten to obtain electrostatic spinning presoma through magnetic stirrer 5~6 hours for liquid (polystyrene-dimethyl formamide solution)
Liquid.Precursor solution is placed in syringe and carries out electrostatic spinning, electrostatic spinning process condition is as follows: voltage 18kV；It receives
Device drum rotation speed is 2000r/min;Receiving distance is 15cm.PS nanofiber obtained is put into vacuum drying oven 2~3 hours,
Finally sampling is in case later period characterization.
PS nanofiber obtained above is soaked in the concentrated sulfuric acid 4 hours, 40 DEG C of progress sulfonating reactions of constant temperature.Reaction terminates
Wash, then filter repeatedly by the homemade distilled water in laboratory, then carry out nearly 12 hours vacuum drying it is spare.After sulfonation
PS (polystyrene) nanofiber be placed in the aniline solution of 0.15molL-1 that (aniline as solute is dissolved in 1molL-1
Hydrochloric acid in), impregnate 12 hours or more, it is therefore an objective to allow the Cation adsorption of aniline in PS Nanosurface.Addition and aniline later
The ammonium persulfate of same molar ratio is placed 24 hours in the environment of 0~5 DEG C, can obtain PANI/PS nano-composite fiber, it
It is washed repeatedly with deionized water again afterwards, suction filtration and vacuum drying.It is small that PANI/PS composite fibre is immersed in tetrahydrofuran 24
When, so that removal nanofiber PS is dissolved, by PANI nanotube can be obtained after washing, suction filtration and drying.
Nanotube fibers PANI 0.2g is taken, 0.05molL is added-1Cobalt chloride hexahydrate 10mL, add 50mL's
Distilled water, then by solution carry out 5min ultrasonication.It is 0.075mol that 25mL concentration is added dropwise in above-mentioned solution
L-1Sodium borohydride, obtained catalyst filtered, washed, and finally drying can obtain the catalyst boronation cobalt on NiB/PANI.
Embodiment 2
With PS(polystyrene) and DMF(N, dinethylformamide) it is raw material, configuration concentration is 12.5wt% PS-DMF solution
(polystyrene-dimethyl formamide solution) obtained electrostatic spinning precursor solution through magnetic stirrer 5~6 hours.
Precursor solution is placed in syringe and carries out electrostatic spinning, electrostatic spinning process condition is as follows: voltage 18kV；Receiver rolling
Cylinder revolving speed is 2000r/min;Receiving distance is 15cm.PS nanofiber obtained is put into vacuum drying oven 2~3 hours, finally
Sampling is in case later period characterization.
PS nanofiber obtained above is soaked in the concentrated sulfuric acid 4 hours, 40 DEG C of progress sulfonating reactions of constant temperature.Reaction terminates
Wash, then filter repeatedly by the homemade distilled water in laboratory, then carry out nearly 12 hours vacuum drying it is spare.After sulfonation
PS (polystyrene) nanofiber be placed in 0.15molL-1Aniline solution in (aniline as solute is dissolved in 1molL-1
Hydrochloric acid in), impregnate 12 hours or more, it is therefore an objective to allow the Cation adsorption of aniline in PS Nanosurface.Addition and aniline later
The ammonium persulfate of same molar ratio is placed 24 hours in the environment of 0~5 DEG C, can obtain PANI/PS nano-composite fiber, it
It is washed repeatedly with deionized water again afterwards, suction filtration and vacuum drying.It is small that PANI/PS composite fibre is immersed in tetrahydrofuran 24
When, so that removal nanofiber PS is dissolved, by PANI nanotube can be obtained after washing, suction filtration and drying.
Nanotube fibers PANI 0.2g is taken, 0.05molL is added-1Cobalt chloride hexahydrate 10mL, add 50mL's
Distilled water, then by solution carry out 5min ultrasonication.It is 0.075mol that 25mL concentration is added dropwise in above-mentioned solution
L-1Sodium borohydride, obtained catalyst filtered, washed, and finally drying can obtain the catalyst boronation cobalt on NiB/PANI.
Embodiment 3
With PS(polystyrene) and DMF(N, dinethylformamide) it is raw material, configuration concentration is that 15.0 wt% PS-DMF are molten
It is molten to obtain electrostatic spinning presoma through magnetic stirrer 5~6 hours for liquid (polystyrene-dimethyl formamide solution)
Liquid.Precursor solution is placed in syringe and carries out electrostatic spinning, electrostatic spinning process condition is as follows: voltage 18kV；It receives
Device drum rotation speed is 2000r/min;Receiving distance is 15cm.PS nanofiber obtained is put into vacuum drying oven 2~3 hours,
Finally sampling is in case later period characterization.
PS nanofiber obtained above is soaked in the concentrated sulfuric acid 4 hours, 40 DEG C of progress sulfonating reactions of constant temperature.Reaction terminates
Wash, then filter repeatedly by the homemade distilled water in laboratory, then carry out nearly 12 hours vacuum drying it is spare.After sulfonation
PS (polystyrene) nanofiber be placed in the aniline solution of 0.15molL-1 that (aniline as solute is dissolved in 1molL-
In 1 hydrochloric acid), impregnate 12 hours or more, it is therefore an objective to allow the Cation adsorption of aniline in PS Nanosurface.Addition and aniline later
The ammonium persulfate of same molar ratio is placed 24 hours in the environment of 0~5 DEG C, can obtain PANI/PS nano-composite fiber, it
It is washed repeatedly with deionized water again afterwards, suction filtration and vacuum drying.It is small that PANI/PS composite fibre is immersed in tetrahydrofuran 24
When, so that removal nanofiber PS is dissolved, by PANI nanotube can be obtained after washing, suction filtration and drying.
Nanotube fibers PANI 0.2g is taken, 0.05molL is added-1Cobalt chloride hexahydrate 10mL, add 50mL's
Distilled water, then by solution carry out 5min ultrasonication.It is 0.075mol that 25mL concentration is added dropwise in above-mentioned solution
L-1Sodium borohydride, obtained catalyst filtered, washed, and finally drying can obtain the catalyst boronation cobalt on NiB/PANI.
Embodiment 4
With PS(polystyrene) and DMF(N, dinethylformamide) it is raw material, configuration concentration is that 25.0 wt% PS-DMF are molten
It is molten to obtain electrostatic spinning presoma through magnetic stirrer 5~6 hours for liquid (polystyrene-dimethyl formamide solution)
Liquid.Precursor solution is placed in syringe and carries out electrostatic spinning, electrostatic spinning process condition is as follows: voltage 18kV；It receives
Device drum rotation speed is 2000r/min;Receiving distance is 15cm.PS nanofiber obtained is put into vacuum drying oven 2~3 hours,
Finally sampling is in case later period characterization.
PS nanofiber obtained above is soaked in the concentrated sulfuric acid 4 hours, 40 DEG C of progress sulfonating reactions of constant temperature.Reaction terminates
Wash, then filter repeatedly by the homemade distilled water in laboratory, then carry out nearly 12 hours vacuum drying it is spare.After sulfonation
PS (polystyrene) nanofiber be placed in 0.15molL-1Aniline solution in (aniline as solute is dissolved in 1molL-1
Hydrochloric acid in), impregnate 12 hours or more, it is therefore an objective to allow the Cation adsorption of aniline in PS Nanosurface.Addition and aniline later
The ammonium persulfate of same molar ratio is placed 24 hours in the environment of 0~5 DEG C, can obtain PANI/PS nano-composite fiber, it
It is washed repeatedly with deionized water again afterwards, suction filtration and vacuum drying.It is small that PANI/PS composite fibre is immersed in tetrahydrofuran 24
When, so that removal nanofiber PS is dissolved, by PANI nanotube can be obtained after washing, suction filtration and drying.
Nanotube fibers PANI 0.2g is taken, 0.05molL is added-1Cobalt chloride hexahydrate 10mL, add 50mL's
Distilled water, then by solution carry out 5min ultrasonication.It is 0.075mol that 25mL concentration is added dropwise in above-mentioned solution
L-1Sodium borohydride, obtained catalyst filtered, washed, and finally drying can obtain the catalyst boronation cobalt on NiB/PANI.
Embodiment 5
With PS(polystyrene) and DMF(N, dinethylformamide) it is raw material, configuration concentration is that 15.0 wt% PS-DMF are molten
It is molten to obtain electrostatic spinning presoma through magnetic stirrer 5~6 hours for liquid (polystyrene-dimethyl formamide solution)
Liquid.Precursor solution is placed in syringe and carries out electrostatic spinning, electrostatic spinning process condition is as follows: voltage 18kV；It receives
Device drum rotation speed is 2000r/min;Receiving distance is 15cm.PS nanofiber obtained is put into vacuum drying oven 2~3 hours,
Finally sampling is in case later period characterization.
PS nanofiber obtained above is soaked in the concentrated sulfuric acid 4 hours, 40 DEG C of progress sulfonating reactions of constant temperature.Reaction terminates
Wash, then filter repeatedly by the homemade distilled water in laboratory, then carry out nearly 12 hours vacuum drying it is spare.After sulfonation
PS (polystyrene) nanofiber be placed in 0.15molL-1Aniline solution in (aniline as solute is dissolved in 1molL-1
Hydrochloric acid in), impregnate 12 hours or more, it is therefore an objective to allow the Cation adsorption of aniline in PS Nanosurface.Addition and aniline later
The ammonium persulfate of same molar ratio is placed 24 hours in the environment of 0~5 DEG C, can obtain PANI/PS nano-composite fiber, it
It is washed repeatedly with deionized water again afterwards, suction filtration and vacuum drying.It is small that PANI/PS composite fibre is immersed in tetrahydrofuran 24
When, so that removal nanofiber PS is dissolved, by PANI nanotube can be obtained after washing, suction filtration and drying.
Nanotube fibers PANI 0.1g is taken, 0.05molL is added-1Cobalt chloride hexahydrate 10mL, add 50mL's
Distilled water, then by solution carry out 5min ultrasonication.It is 0.075mol that 25mL concentration is added dropwise in above-mentioned solution
L-1Sodium borohydride, obtained catalyst filtered, washed, and finally drying can obtain the catalyst boronation cobalt on NiB/PANI.
Embodiment 6
With PS(polystyrene) and DMF(N, dinethylformamide) it is raw material, configuration concentration is that 15.0 wt% PS-DMF are molten
It is molten to obtain electrostatic spinning presoma through magnetic stirrer 5~6 hours for liquid (polystyrene-dimethyl formamide solution)
Liquid.Precursor solution is placed in syringe and carries out electrostatic spinning, electrostatic spinning process condition is as follows: voltage 18kV；It receives
Device drum rotation speed is 2000r/min;Receiving distance is 15cm.PS nanofiber obtained is put into vacuum drying oven 2~3 hours,
Finally sampling is in case later period characterization.
PS nanofiber obtained above is soaked in the concentrated sulfuric acid 4 hours, 40 DEG C of progress sulfonating reactions of constant temperature.Reaction terminates
Wash, then filter repeatedly by the homemade distilled water in laboratory, then carry out nearly 12 hours vacuum drying it is spare.After sulfonation
PS (polystyrene) nanofiber be placed in 0.15molL-1Aniline solution in (aniline as solute is dissolved in 1molL-1
Hydrochloric acid in), impregnate 12 hours or more, it is therefore an objective to allow the Cation adsorption of aniline in PS Nanosurface.Addition and aniline later
The ammonium persulfate of same molar ratio is placed 24 hours in the environment of 0~5 DEG C, can obtain PANI/PS nano-composite fiber, it
It is washed repeatedly with deionized water again afterwards, suction filtration and vacuum drying.It is small that PANI/PS composite fibre is immersed in tetrahydrofuran 24
When, so that removal nanofiber PS is dissolved, by PANI nanotube can be obtained after washing, suction filtration and drying.
Nanotube fibers PANI 0.3g is taken, 0.05molL is added-1Cobalt chloride hexahydrate 10mL, add 50mL's
Distilled water, then by solution carry out 5min ultrasonication.It is 0.075mol that 25mL concentration is added dropwise in above-mentioned solution
L-1Sodium borohydride, obtained catalyst filtered, washed, and finally drying can obtain the catalyst boronation cobalt on NiB/PANI.
NiB/PANI nanofiber pipe composite catalyst is applied in preparing hydrogen by sodium borohydride hydrolysis technology.
It is to be understood that being merely to illustrate the present invention above with respect to specific descriptions of the invention and being not limited to this
Technical solution described in inventive embodiments, those skilled in the art should understand that, still the present invention can be carried out
Modification or equivalent replacement, to reach identical technical effect；As long as meet use needs, all protection scope of the present invention it
It is interior.
Claims (10)
1. a kind of preparation method of NiB/PANI nano-fiber catalyst, which comprises the steps of:
(1) using polystyrene and n,N-Dimethylformamide as raw material, polystyrene is taken to be dissolved in n,N-Dimethylformamide,
It is made into electrostatic spinning precursor solution A；
(2) precursor solution A obtained by step (1) is placed in syringe, polystyrene nano fiber B is made in electrostatic spinning；
(3) nanofiber B obtained by step (2) is immersed in the concentrated sulfuric acid, carries out sulfonation processing, is received to obtain sulfonated polystyrene
Rice, then it is rinsed well to be placed in baking oven be dried to obtain nanofiber C with deionized water；
(4) nanofiber C obtained by step (3) is soaked in aniline solution, ammonium persulfate is then added and reacts at low temperature, obtains
To composite nano fiber D；
(5) composite nano fiber D obtained by step (4) is soaked in removal polystyrene kernel in tetrahydrofuran and obtains nanotube E；
(6) nanotube E obtained by step (5) is immersed in nickel source aqueous solution, is then NiB with sodium borohydride reduction nickel source, i.e.,
Obtain target product NiB/PANI nano-tube composite catalyst.
2. the preparation method of NiB/PANI nano-fiber catalyst according to claim 1, it is characterised in that: the step
(6) nickel source is Nickel dichloride hexahydrate (II) in.
3. the preparation method of NiB/PANI nano-fiber catalyst according to claim 2, it is characterised in that: the step
(1) in, the mass ratio of n,N-Dimethylformamide and polystyrene is 100:10~20.
4. the preparation method of NiB/PANI nano-fiber catalyst according to claim 3, it is characterised in that: the step
(3) in, 40oC carries out sulfonation processing to obtain sulfonated polystyrene nanometer.
5. the preparation method of NiB/PANI nano-fiber catalyst according to claim 4, it is characterised in that: the step
(4) in, the low temperature lower reaction time is for 24 hours；The mass ratio of the ammonium persulfate and ammonium sulfate is 1:1.
6. the preparation method of NiB/PANI nano-fiber catalyst according to claim 5, it is characterised in that: the step
(2) in, electrospinning conditions: voltage 18kV；Receiver drum rotation speed is 2000r/min；Receiving distance is 15cm；It will be made
Polystyrene nano fiber B be put into vacuum drying oven 2~3 hours.
7. the preparation method of NiB/PANI nano-fiber catalyst according to claim 6, it is characterised in that: by step
(2) gained nanofiber B immerses in the concentrated sulfuric acid 4 hours, 40 DEG C of progress sulfonating reactions of constant temperature.
8. the preparation method of NiB/PANI nano-fiber catalyst according to claim 7, it is characterised in that: the step
(4) in, nanofiber C obtained by step (3) is soaked in aniline solution, soaking time is 12 hours or more.
9. the preparation method of NiB/PANI nano-fiber catalyst according to claim 7, it is characterised in that: the step
(4) in, ammonium persulfate is added and is reacted 24 hours under 0~5 DEG C of environment, obtains composite nano fiber D.
10. a kind of application of NiB/PANI nano-fiber catalyst in preparing hydrogen by sodium borohydride hydrolysis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811546056.1A CN109647534A (en) | 2018-12-18 | 2018-12-18 | A kind of preparation method of NiB/PANI nano-fiber catalyst and its application in preparing hydrogen by sodium borohydride hydrolysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811546056.1A CN109647534A (en) | 2018-12-18 | 2018-12-18 | A kind of preparation method of NiB/PANI nano-fiber catalyst and its application in preparing hydrogen by sodium borohydride hydrolysis |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109647534A true CN109647534A (en) | 2019-04-19 |
Family
ID=66113545
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811546056.1A Pending CN109647534A (en) | 2018-12-18 | 2018-12-18 | A kind of preparation method of NiB/PANI nano-fiber catalyst and its application in preparing hydrogen by sodium borohydride hydrolysis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109647534A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110687164A (en) * | 2019-09-16 | 2020-01-14 | 深圳市立洋光电子股份有限公司 | Pt-In2O3Preparation method of nano material and gas sensor |
| CN114100614A (en) * | 2021-12-06 | 2022-03-01 | 桂林电子科技大学 | Co-Cu-B nanoparticle-loaded composite material of hollow carbon material and preparation method and application thereof |
| CN114700105A (en) * | 2022-05-17 | 2022-07-05 | 桂林电子科技大学 | Co-Mo-B/N-PCN composite nano material and preparation method and application thereof |
| CN115702268A (en) * | 2020-05-11 | 2023-02-14 | Ddp特种电子材料美国有限责任公司 | Sulfonated polystyrene nonwovens |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104353497A (en) * | 2014-11-13 | 2015-02-18 | 辽宁石油化工大学 | Preparing method and application of NiB/PVDF (polyvinylidene fluoride) nano-fiber catalyst |
| HUP1400227A2 (en) * | 2014-05-06 | 2016-01-28 | Hydro Tar Kft | Process for producing hydrogen from metal borohydride with catalyst by hydrolysis |
-
2018
- 2018-12-18 CN CN201811546056.1A patent/CN109647534A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HUP1400227A2 (en) * | 2014-05-06 | 2016-01-28 | Hydro Tar Kft | Process for producing hydrogen from metal borohydride with catalyst by hydrolysis |
| CN104353497A (en) * | 2014-11-13 | 2015-02-18 | 辽宁石油化工大学 | Preparing method and application of NiB/PVDF (polyvinylidene fluoride) nano-fiber catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 马小玉: "静电纺制备聚苯胺/贵金属纳米管复合物修饰电极及其电分析应用", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110687164A (en) * | 2019-09-16 | 2020-01-14 | 深圳市立洋光电子股份有限公司 | Pt-In2O3Preparation method of nano material and gas sensor |
| CN115702268A (en) * | 2020-05-11 | 2023-02-14 | Ddp特种电子材料美国有限责任公司 | Sulfonated polystyrene nonwovens |
| CN114100614A (en) * | 2021-12-06 | 2022-03-01 | 桂林电子科技大学 | Co-Cu-B nanoparticle-loaded composite material of hollow carbon material and preparation method and application thereof |
| CN114700105A (en) * | 2022-05-17 | 2022-07-05 | 桂林电子科技大学 | Co-Mo-B/N-PCN composite nano material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109647534A (en) | A kind of preparation method of NiB/PANI nano-fiber catalyst and its application in preparing hydrogen by sodium borohydride hydrolysis | |
| Xu et al. | Cobalt nanoparticles encapsulated in nitrogen-doped carbon shells: efficient and stable catalyst for nitrobenzene reduction | |
| Ren et al. | One-pot synthesis of carbon nanofibers from CO2 | |
| Xu et al. | Methanol electrocatalytic oxidation on Pt nanoparticles on nitrogen doped graphene prepared by the hydrothermal reaction of graphene oxide with urea | |
| Zhao et al. | Ionic liquid assisted preparation of phosphorus-doped g-C3N4 photocatalyst for decomposition of emerging water pollutants | |
| CN102350499B (en) | Cu/Cu2O core-shell composite microsphere and preparation method thereof | |
| Cai et al. | Bridging effect of Co heteroatom between g-C3N4 and Pt NPs for enhanced photocatalytic hydrogen evolution | |
| CN102078811B (en) | Method for preparing carbon loading Pd nanometer particle catalyst by using homogeneous precipitation-reduction in situ method | |
| Wang et al. | Photoinduced homogeneous RuO2 nanoparticles on TiO2 nanowire arrays: A high-performance cathode toward flexible Li–CO2 batteries | |
| Ding et al. | Thermal conversion of hollow nickel-organic framework into bimetallic FeNi3 alloy embedded in carbon materials as efficient oer electrocatalyst | |
| CN103691480B (en) | A kind of preparation technology of preparing hydrogen by sodium borohydride hydrolysis catalyst | |
| CN104372434A (en) | Preparation method of PAN/CoCl2/CNTs composite nano fibers and application of PAN/CoCl2/CNTs composite nano fibers to NaBH4 hydrogen production | |
| Wang et al. | Highly phosphatized magnetic catalyst with electron transfer induced by quaternary synergy for efficient dehydrogenation of ammonia borane | |
| Yue et al. | Coral-like Au/TiO2 hollow nanofibers with through-holes as a high-efficient catalyst through mass transfer enhancement | |
| CN104707590B (en) | A kind of preparation method and applications of morphology controllable indium nanocatalyst | |
| Zhang et al. | Deep eutectic solvent-mediated hierarchically structured Fe-based organic–inorganic hybrid catalyst for oxygen evolution reaction | |
| CN103657643A (en) | Method for preparing nano palladium metal catalyst | |
| Jia et al. | Assembly and superior performance of palladium nano-catalysts anchored to a magnetic konjac glucomannan-graphene oxide hybrid for H2 generation from ammonia borane | |
| CN105006379A (en) | Ruthenium dioxide nanometer cluster/carbon composite material and preparation method thereof | |
| Zhang et al. | N-Doped porous carbon supported palladium nanoparticles as a highly efficient and recyclable catalyst for the Suzuki coupling reaction | |
| Wan et al. | One-dimensional ternary Ag@ Ag2S@ C nanocable with plasmon-enhanced photocatalytic performance | |
| Xu et al. | Batch preparation of CuO/ZnO-loaded nanofiber membranes for photocatalytic degradation of organic dyes | |
| Gopiraman et al. | Preparation, characterization, and applications of electrospun carbon Nanofibers and its composites | |
| Yang et al. | Nanofabrication of Ni-incorporated three-dimensional ordered mesoporous carbon for catalytic methane decomposition | |
| CN104353497A (en) | Preparing method and application of NiB/PVDF (polyvinylidene fluoride) nano-fiber catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190419 |
|
| RJ01 | Rejection of invention patent application after publication |