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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 PDF

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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
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nib
nanofibers
pani
polystyrene
preparation
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邓雨钊
李其明
李芳�
刘力魁
李佳
刘文博
孙爱玲
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Liaoning Shihua University
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    • 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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • 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

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  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
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Abstract

本发明属合成复合催化剂领域，特别涉及一种NiB/PANI纳米纤维催化剂的制备方法及其在硼氢化钠水解制氢中的应用，包括如下步骤：（1）取聚苯乙烯溶于N,N‑二甲基甲酰胺中，配成静电纺丝前驱体溶液A；（2）制得聚苯乙烯纳米纤维B；（3）将纳米纤维B浸入浓硫酸中，得到磺化聚苯乙烯纳米，然后将其冲洗干燥得到纳米纤维C；（4）将纳米纤维C浸泡于苯胺溶液中，加入过硫酸铵反应，得到复合纳米纤维D；（5）将复合纳米纤维D浸泡于四氢呋喃中得到纳米管E；（6）将纳米管E浸泡在镍源水溶液中，还原镍源为NiB，即得目标产物。本发明投资成本低廉，催化剂比表面积大，分散性好，稳定性高，可重复多次使用，并且易于回收。

The invention belongs to the field of synthetic composite catalysts, and in particular relates to a preparation method of a NiB/PANI nanofiber catalyst and its application in hydrogen production by hydrolysis of sodium borohydride, comprising the following steps: (1) dissolving polystyrene in N,N -Dimethylformamide, prepare electrospinning precursor solution A; (2) prepare polystyrene nanofibers B; (3) immerse nanofibers B in concentrated sulfuric acid to obtain sulfonated polystyrene nanofibers, Then rinse and dry to obtain nanofibers C; (4) soak nanofibers C in aniline solution, add ammonium persulfate to react to obtain composite nanofibers D; (5) soak composite nanofibers D in tetrahydrofuran to obtain nanotubes E; (6) The nanotube E is soaked in the nickel source aqueous solution, and the nickel source is reduced to NiB to obtain the target product. The invention has the advantages of low investment cost, large catalyst specific surface area, good dispersibility, high stability, repeated use and easy recovery.

Description

The preparation method of a kind of NiB/PANI nano-fiber catalyst and its in sodium borohydride water Solve the application in hydrogen manufacturing
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)

1.一种NiB/PANI纳米纤维催化剂的制备方法，其特征在于，包括如下步骤：1. a preparation method of NiB/PANI nanofiber catalyst, is characterized in that, comprises the steps: （1）以聚苯乙烯及N, N-二甲基甲酰胺为原料，取聚苯乙烯溶于N, N-二甲基甲酰胺中，配成静电纺丝前驱体溶液A；(1) Using polystyrene and N, N-dimethylformamide as raw materials, dissolving polystyrene in N, N-dimethylformamide to prepare electrospinning precursor solution A; （2）将步骤（1）所得前驱体溶液A置于注射器中，静电纺丝制得聚苯乙烯纳米纤维B；(2) placing the precursor solution A obtained in step (1) in a syringe, and electrospinning to obtain polystyrene nanofibers B; （3）将步骤（2）所得纳米纤维B浸入浓硫酸中，进行磺化处理，从而得到磺化聚苯乙烯纳米，然后将其用去离子水冲洗干净并置于烘箱中干燥得到纳米纤维C；(3) Immerse the nanofibers B obtained in step (2) in concentrated sulfuric acid and perform sulfonation treatment to obtain sulfonated polystyrene nanometers, which are then rinsed with deionized water and dried in an oven to obtain nanofibers C ; （4）将步骤（3）所得纳米纤维C浸泡于苯胺溶液中，然后加入过硫酸铵在低温下反应，得到复合纳米纤维D；(4) soaking the nanofibers C obtained in step (3) in an aniline solution, and then adding ammonium persulfate to react at low temperature to obtain composite nanofibers D; （5）将步骤（4）所得复合纳米纤维D浸泡于四氢呋喃中去除聚苯乙烯内核得到纳米管E；(5) soaking the composite nanofibers D obtained in step (4) in tetrahydrofuran to remove the polystyrene core to obtain nanotubes E; （6）将步骤（5）所得纳米管E浸泡在镍源水溶液中，然后用硼氢化钠还原镍源为NiB，即得目标产物NiB/PANI纳米管复合催化剂。(6) Immerse the nanotubes E obtained in step (5) in a nickel source aqueous solution, and then reduce the nickel source to NiB with sodium borohydride to obtain the target product NiB/PANI nanotube composite catalyst. 2.根据权利要求1所述的NiB/PANI纳米纤维催化剂的制备方法，其特征在于：所述步骤（6）中镍源为六水合氯化镍（Ⅱ）。2 . The preparation method of NiB/PANI nanofiber catalyst according to claim 1 , wherein the nickel source in the step (6) is nickel chloride hexahydrate (II). 3 . 3.根据权利要求2所述的NiB/PANI纳米纤维催化剂的制备方法，其特征在于：所述步骤（1）中，N, N-二甲基甲酰胺与聚苯乙烯的质量比为100: 10～20。3. the preparation method of NiB/PANI nanofiber catalyst according to claim 2, is characterized in that: in described step (1), the mass ratio of N, N-dimethylformamide and polystyrene is 100: 10 to 20. 4.根据权利要求3所述的NiB/PANI纳米纤维催化剂的制备方法，其特征在于：所述步骤（3）中，在40oC进行磺化处理从而得到磺化聚苯乙烯纳米。4 . The preparation method of NiB/PANI nanofiber catalyst according to claim 3 , wherein in the step (3), sulfonation treatment is performed at 40 ℃ to obtain sulfonated polystyrene nanometers. 5 . 5.根据权利要求4所述的NiB/PANI纳米纤维催化剂的制备方法，其特征在于：所述步骤（4）中，低温下反应时间为24h；所述过硫酸铵与硫酸铵的质量比为1:1。5. The preparation method of NiB/PANI nanofiber catalyst according to claim 4, characterized in that: in the step (4), the reaction time at low temperature is 24h; the mass ratio of the ammonium persulfate to the ammonium sulfate is 1:1. 6.根据权利要求5所述的NiB/PANI纳米纤维催化剂的制备方法，其特征在于：所述步骤（2）中，静电纺丝条件：电压为18kV；接收器滚筒转速为2000r/min；接收距离为15cm；将制得的聚苯乙烯纳米纤维B放入真空烘箱2～3小时。The preparation method of NiB/PANI nanofiber catalyst according to claim 5, characterized in that: in the step (2), the electrospinning conditions: the voltage is 18kV; the rotating speed of the receiver drum is 2000r/min; The distance is 15 cm; the prepared polystyrene nanofibers B are placed in a vacuum oven for 2-3 hours. 7.根据权利要求6所述的NiB/PANI纳米纤维催化剂的制备方法，其特征在于：将步骤（2）所得纳米纤维B浸入浓硫酸中4小时，恒温40℃进行磺化反应。7 . The preparation method of NiB/PANI nanofiber catalyst according to claim 6 , wherein the nanofibers B obtained in step (2) are immersed in concentrated sulfuric acid for 4 hours, and the sulfonation reaction is carried out at a constant temperature of 40° C. 8 . 8.根据权利要求7所述的NiB/PANI纳米纤维催化剂的制备方法，其特征在于：所述步骤（4）中，将步骤（3）所得纳米纤维C浸泡于苯胺溶液中，浸泡时间为12小时以上。The preparation method of NiB/PANI nanofiber catalyst according to claim 7, characterized in that: in the step (4), the nanofibers C obtained in the step (3) are soaked in an aniline solution for a soaking time of 12 hours or more. 9.根据权利要求7所述的NiB/PANI纳米纤维催化剂的制备方法，其特征在于：所述步骤（4）中，加入过硫酸铵在0～5℃环境下反应24小时，得到复合纳米纤维D。9 . The preparation method of NiB/PANI nanofiber catalyst according to claim 7 , characterized in that: in the step (4), ammonium persulfate is added to react for 24 hours at 0 to 5° C. to obtain composite nanofibers. 10 . D. 10.一种NiB/PANI纳米纤维催化剂在硼氢化钠水解制氢中的应用。10. Application of a NiB/PANI nanofiber catalyst in the hydrolysis of sodium borohydride to hydrogen production.
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Cited By (4)

* Cited by examiner, † Cited by third party
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 A kind of composite material of hollow carbon material supporting Co-Cu-B nanoparticles and its preparation method and application
CN114700105A (en) * 2022-05-17 2022-07-05 桂林电子科技大学 A Co-Mo-B/N-PCN composite nanomaterial and its preparation method and application
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)

* Cited by examiner, † Cited by third party
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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 A kind of composite material of hollow carbon material supporting Co-Cu-B nanoparticles and its preparation method and application
CN114700105A (en) * 2022-05-17 2022-07-05 桂林电子科技大学 A Co-Mo-B/N-PCN composite nanomaterial and its preparation method and application

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