CN106410214A - Preparation method of NiS2 catalyst with high specific surface area - Google Patents

Preparation method of NiS2 catalyst with high specific surface area Download PDF

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Publication number
CN106410214A
CN106410214A CN201610820849.2A CN201610820849A CN106410214A CN 106410214 A CN106410214 A CN 106410214A CN 201610820849 A CN201610820849 A CN 201610820849A CN 106410214 A CN106410214 A CN 106410214A
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China
Prior art keywords
catalyst
surface area
specific surface
nis
nis2
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CN201610820849.2A
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石文娟
张亚彬
余建国
赵永男
覃发梅
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Tianjin Polytechnic University
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Tianjin Polytechnic University
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Priority to CN201610820849.2A priority Critical patent/CN106410214A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • H01M8/1013—Other direct alcohol fuel cells [DAFC]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Inert Electrodes (AREA)

Abstract

The present invention discloses a preparation method of an NiS2 catalyst with a high specific area. The method comprises the following steps of mixing and dispersing sodium sulfide and nickel chloride in a water solution, adjusting pH of the solution, stirring, heating by water, filtering, washing and stoving to obtain the NiS2 catalyst with high specific surface area. The specific surface area of the NiS2 catalyst prepared by the method can reach 215.8m<2>g<1>, so that high specific surface area is beneficial for improving the electrocatalysis performance of the catalyst for ethanol oxidization in a sodium hydroxide solution, and facilitates mass transfer. The raw material of the NiS2 catalyst is low-cost, the preparation method is simple, and the NiS2 catalyst is a novel high-performance catalyst directly used as the ethanol fuel battery anode.

Description

A kind of NiS of high-specific surface area2The preparation method of catalyst
Technical field
The present invention relates to a kind of preparation method of Catalytic oxidation of ethanol agent is and in particular to a kind of NiS of high-specific surface area2Urge The preparation method of agent.
Background technology
In the last few years, energy shortage and environmental pollution were two hang-ups that the world today faces, and direct fuel cell is with it Have the advantages that fuel source is wide, the high and low pollution of energy transformation ratio, storage and convenient transportation, in compact power, electric motor car Have broad application prospects in field, have been obtained for worldwide concern and pay attention to.Direct liquid fuel battery is permissible Make fuel using methanol, but methanol has certain toxicity it is therefore necessary to the new liquid of exploration can to substitute poisonous methanol, ethanol Regeneration, and nontoxic, abundance, use safety, practical application has a high potential, and can substitute DMFC.But, The activity of electrode elctro-catalyst is relatively low and fancy price is still to hinder one of key issue of commercializing fuel cells development.Carry High catalyst activity, reduction noble metal dosage are the important channels promoting commercializing fuel cells development.
At present, the Direct Ethanol Fuel Cell catalyst of most study is still platinum and palladium class material.Wang et al. uses carbon fine Wei Bu support palladium-cobalt nano-tube array is catalyst, electrocatalytic oxidation ethanol.(Angewandte Chemie International Edition, 2015,54 (12)：3669-3673) these material resources are rare, expensive, and are catalyzed During easily poisoning lead to catalysis activity to reduce, service life is short, and the application of its large-scale commercial receives serious restriction.
Therefore, so that catalyst electro catalytic activity is improved, cost more reduces, be Direct Ethanol Fuel Cell research and development Important content.However, the specific surface area of catalyst is one important key factor of catalysis activity.Because higher specific surface area side Just mass transfer and diffusion.For example, Wang et al. devises layering NiCo2O4@Ni3S2Core shell array has high-specific surface area, low The electric capacity that charge-transfer resistance is become reconciled.(Journal of Materials Chemistry A2(2014)17595-17601) Das et al. is by NiCo2O4It is supported on the performance that electrocatalytic oxidation ethanol is improved on Graphene.(Nanoscale, 2014,6 (18)： 10657-10665) present invention defines a kind of non-precious metal catalyst using sodium sulfide and Nickel dichloride., and this is to the direct ethanol of raising Fuel cell equal energy source conversion equipment commercialized development is significant.
Content of the invention
It is an object of the invention to provide a kind of NiS of high-specific surface area2The preparation method of catalyst, the catalyst of preparation Oxidation of ethanol catalysis activity and long-time stability are increased, and the ethanol applied in practical process is cheap, convenient Carry, and nontoxic, possess higher practical value.
A kind of NiS of the high-specific surface area of the present invention2The preparation method of catalyst comprises the following steps：By sodium sulfide, chlorine Change nickel and water with mass ratio 1: 0.2～0.6: 20 mixing dispersion in aqueous, and adjust pH 4～7, mixing time 1～ 2h, carries out hydro-thermal afterwards, and hydrothermal temperature is 120～160 DEG C, and the hydro-thermal time keeps 8～12h, the sample filtering after hydro-thermal, so After put in distilled water and boil, filtration washing, to neutral, obtains the NiS of high-specific surface area in 60～100 DEG C of drying 1～10h2 Catalyst.NiS herein2The specific surface area of catalyst can reach 215.8m2g-1, also more mesoporous be conducive to mass transfer, carry High electrocatalysis characteristic.
Brief description
In order that the purpose of the present invention, technical scheme and beneficial effect become apparent from, the present invention provides drawings described below to carry out Explanation：
Fig. 1 is the NiS of the high-specific surface area of embodiment 1 preparation2The SEM figure of catalyst；
Fig. 2 is the NiS of the high-specific surface area of embodiment 1 preparation2The XRD figure of catalyst；
Fig. 3 is the NiS of the high-specific surface area of embodiment 1 preparation2Catalyst is in 0.1M NaOH+0.5M C2H5In OH solution Cyclic voltammetry curve figure；
Fig. 4 is the NiS of the high-specific surface area of embodiment 1 preparation2The nitrogen adsorption desorption curve chart of catalyst.
Specific embodiment
Embodiment 1
A kind of NiS of high-specific surface area2Method for preparing catalyst, comprises the steps：Respectively by 1.6g sodium sulfide, 0.7g Nickel dichloride. and 70ml water are placed in 100ml beaker, and adjust pH to 4, and mixing time 2h carries out hydro-thermal, hydrothermal temperature afterwards For 120, hydro-thermal time holding 10h, the sample filtering after hydro-thermal, it is then placed in boiling in distilled water, filtration washing is extremely neutral, NiS that 10h obtain high-specific surface area is dried in 60 DEG C2Catalyst.Fig. 1 is the NiS preparing high-specific surface area2The SEM of catalyst Figure.Significantly find out nanosphere from figure, and these balls are to pile up with little particle to form, dispersion ratio is more uniform.Fig. 2 is catalysis The XRD figure of agent.To in XRD figure analysis, respectively at 31.5 °, 35.3 °, 38.8 °, 45.1 ° and 53.5 ° correspond respectively to peak value NiS2(200), (210), (211), (220) and (311) crystal face, illustrate to have obtained high ratio by the preparation method of embodiment 1 The NiS of surface area2Catalyst.Fig. 3 is catalyst in 0.1M NaOH+0.5M C2H5Cyclic voltammetry curve figure in OH solution.Can To find out the NiS of high-specific surface area2Catalyst shows high electric current density (45mA cm-2) and high specific surface area (215.8m2g-1), the NiS of the high-specific surface area of embodiment 1 preparation is described2Catalyst has excellent oxidation of ethanol catalytic Can, and by ampere during tester, very high reaction rate can be obtained.After circulation 500 circle, remain to keep steady well Qualitative.
Embodiment 2
A kind of NiS of high-specific surface area2Method for preparing catalyst, comprises the steps：Respectively by 1.6g sodium sulfide, 0.7g Nickel dichloride. and 70ml water are placed in 100ml beaker, and adjust pH to 5, and mixing time 2h carries out hydro-thermal, hydrothermal temperature afterwards For 120, hydro-thermal time holding 10h, the sample filtering after hydro-thermal, it is then placed in boiling in distilled water, filtration washing is extremely neutral, NiS that 10h obtain high-specific surface area is dried in 60 DEG C2Catalyst.With the method preparation catalyst with respect to example 1 Say, the comparison of particle agglomeration is severe, and skewness, electric current density (37mA cm-2) and specific surface area (130.2m2g-1) It is decreased obviously, its electrocatalysis characteristic is not especially good.
The above is only the concrete application example of the present invention, protection scope of the present invention is not limited in any way, at this In the range of the mass ratio of each component employed in bright technical scheme, some modification and improvement can also be made, these modification and Improve and also should be regarded as protection scope of the present invention.

Claims (7)

1. the NiS of high-specific surface area2The preparation method of catalyst it is characterised in that：Comprise the following steps：By sodium sulfide, Nickel dichloride. Mixing disperses in aqueous, and adjusts the pH of solution, stirring, and hydro-thermal filters, clean drying can get high-specific surface area NiS2Catalyst.
2. the NiS of high-specific surface area according to claim 12Catalyst it is characterised in that described sodium sulfide, Nickel dichloride. and The mass ratio 1: 0.2～0.6: 20 of water.
3. the NiS of high-specific surface area according to claim 12It is characterised in that adjusting pH 4～7, temperature is catalyst Room temperature.
4. the NiS of high-specific surface area according to claim 12Catalyst is it is characterised in that mixing time 1～2h, temperature For room temperature.
5. the NiS of high-specific surface area according to claim 12Catalyst is it is characterised in that hydrothermal temperature is 120～160 DEG C, the hydro-thermal time keeps 8～12h.
6. the NiS of high-specific surface area according to claim 12Catalyst, described clean drying course is：After hydro-thermal Sample filtering, put in distilled water afterwards and boil, filtration washing to neutral, then 60～100 DEG C of drying 1～10h.
7. NiS according to prepared by claim 1-62Specific surface area of catalyst reaches 215.8m2g-1, high specific surface area is conducive to Mass transfer and diffusion, and the electrocatalysis characteristic of ethanol can be improved.During electro-catalysis, show high electric current density ( 0.1M NaOH+.0.5M C2H5In OH, electric current density can reach 45mA cm-2) and good stability (after circulation 500 circle, In new electrolyte, electric current density remains to keep 90.1%).These good performances are closely bound up with the structure of catalyst. High-specific surface area and purer NiS can be prepared by this method2.
CN201610820849.2A 2016-09-12 2016-09-12 Preparation method of NiS2 catalyst with high specific surface area Pending CN106410214A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107754840A (en) * 2017-10-20 2018-03-06 天津工业大学 One-step method prepares the N doping platinum nickel carbon electrochemical catalyst for Catalytic oxidation of ethanol
CN108315730A (en) * 2018-01-29 2018-07-24 燕山大学 A kind of in-situ preparation method of prism-shaped nickel sulfide array film material
CN109277104A (en) * 2018-10-16 2019-01-29 陕西科技大学 A kind of NiS of sulfur-rich vanadium modification2Elctro-catalyst and preparation method thereof
CN110993971A (en) * 2019-12-12 2020-04-10 电子科技大学 NiS2/ZnIn2S4Composite material and preparation method and application thereof
CN111348690A (en) * 2020-03-13 2020-06-30 南京邮电大学 NiS2Nano material and preparation method thereof
CN111362320A (en) * 2020-03-13 2020-07-03 江西师范大学 Loaded nickel sulfide nanorod material and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1690262A (en) * 2004-04-23 2005-11-02 中国科学院理化技术研究所 Micro carbon roll and preparation method and application thereof
CN102633309A (en) * 2012-01-13 2012-08-15 沈阳理工大学 Hydrothermal preparation method for NiS2 with controllable shape
CN105449171A (en) * 2016-01-05 2016-03-30 北京金吕能源科技有限公司 Preparation method of nanometer nickel sulfide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1690262A (en) * 2004-04-23 2005-11-02 中国科学院理化技术研究所 Micro carbon roll and preparation method and application thereof
CN102633309A (en) * 2012-01-13 2012-08-15 沈阳理工大学 Hydrothermal preparation method for NiS2 with controllable shape
CN105449171A (en) * 2016-01-05 2016-03-30 北京金吕能源科技有限公司 Preparation method of nanometer nickel sulfide

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107754840A (en) * 2017-10-20 2018-03-06 天津工业大学 One-step method prepares the N doping platinum nickel carbon electrochemical catalyst for Catalytic oxidation of ethanol
CN108315730A (en) * 2018-01-29 2018-07-24 燕山大学 A kind of in-situ preparation method of prism-shaped nickel sulfide array film material
CN108315730B (en) * 2018-01-29 2020-05-12 燕山大学 In-situ preparation method of prismatic nickel sulfide array film material
CN109277104A (en) * 2018-10-16 2019-01-29 陕西科技大学 A kind of NiS of sulfur-rich vanadium modification2Elctro-catalyst and preparation method thereof
CN109277104B (en) * 2018-10-16 2021-08-06 陕西科技大学 Sulfur-rich vanadium-modified NiS2Electrocatalyst and method of making
CN110993971A (en) * 2019-12-12 2020-04-10 电子科技大学 NiS2/ZnIn2S4Composite material and preparation method and application thereof
CN110993971B (en) * 2019-12-12 2022-07-29 电子科技大学 NiS 2 /ZnIn 2 S 4 Composite material and preparation method and application thereof
CN111348690A (en) * 2020-03-13 2020-06-30 南京邮电大学 NiS2Nano material and preparation method thereof
CN111362320A (en) * 2020-03-13 2020-07-03 江西师范大学 Loaded nickel sulfide nanorod material and preparation method and application thereof
CN111348690B (en) * 2020-03-13 2023-08-11 南京邮电大学 NiS (nickel-zinc sulfide) 2 Nanomaterial and preparation method thereof

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Application publication date: 20170215