CN110359059A - Electro-catalysis produces oxygen NiPS3/ graphene composite catalyst and preparation method thereof - Google Patents

Electro-catalysis produces oxygen NiPS3/ graphene composite catalyst and preparation method thereof Download PDF

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CN110359059A
CN110359059A CN201810321934.3A CN201810321934A CN110359059A CN 110359059 A CN110359059 A CN 110359059A CN 201810321934 A CN201810321934 A CN 201810321934A CN 110359059 A CN110359059 A CN 110359059A
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nips
nanometer sheet
composite catalyst
graphene
electro
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CN110359059B (en
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任文才
薛森
陈龙
成会明
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Institute of Metal Research of CAS
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • 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 electro-catalysis fields, and in particular to a kind of electro-catalysis production oxygen NiPS3/ graphene composite catalyst and preparation method thereof.Using the NiPS of vapor transportation method preparation large scale, high quality3Crystal, Tip ultrasound obtains a small number of layer NiPS in water3The dispersion liquid of nanometer sheet mixes ultrasound with commercial graphene powder after vacuum filtration is dry, obtains NiPS3/ graphene composite catalyst, the composite catalyst preparation process have the characteristics that method is simple, is easy amplification, is at low cost.The present invention makes full use of NiPS3The features such as high-specific surface area, satisfactory electrical conductivity of excellent electro-catalysis production oxygen activity and graphene, solve NiPS3Poorly conductive and the non-uniform problem of dispersion, so that electro-catalysis can be realized under lower loading and produce the lower take-off potential of oxygen, lesser Tafel slope, high job stability and only need smaller overpotential that can obtain higher current density for the composite catalyst, excellent electrocatalysis characteristic is realized.

Description

Electro-catalysis produces oxygen NiPS3/ graphene composite catalyst and preparation method thereof
Technical field:
The invention belongs to electro-catalysis fields, and in particular to a kind of electro-catalysis production oxygen NiPS3/ graphene composite catalyst and its Preparation method.
Background technique:
Electrolysis water is presently the most efficiently, cleans one of method of hydrogen manufacturing.Two half-reactions of electrolysis water produce hydrogen reaction (HER) and the reaction energy barrier of production oxygen reaction (OER) is higher, generally requires addition catalyst to accelerate electrochemical reaction speed.And Oxygen reaction (OER) is produced due to being four electron reaction processes, kinetics process is more than production hydrogen reaction (HER) difficulty.Therefore, Produce the limited reactions that oxygen reaction (OER) is considered as electrolysis water.Currently, metal oxide containing precious metals such as ruthenium-oxide (RuO2) and yttrium oxide (IrO2) be the highest OER catalyst of activity, but since noble metal reserves are limited, expensive, stability is poor etc., these because Element restricts its commercial applications.Therefore, the novel non-noble metal OER catalyst of developing low-cost is to solve water electrolysis hydrogen production, system One of oxygen energy consumption height, the important channel of low yield.
Compared to block materials, two-dimensional material has higher specific surface area, more boundary sites, the electricity for being easy to regulate and control Minor structure and the advantages that be easier to functionalization.Wherein, graphene be by single layer of carbon atom it is tightly packed at bi-dimensional cellular Shape crystal has excellent electricity, calorifics and mechanical property, is widely used as catalyst or the substrate of other active materials Dispersion is applied to electro-catalysis field.Stratified material transition metal sulfur phosphorus compound MPS3(M=Fe, Co, Ni etc.) is being electrolysed Water field also receives significant attention, wherein NiPS3It shows preferable electro-catalysis and produces oxygen catalytic performance, but its poor conductance Rate and dispersibility seriously restrict its practical application.
Summary of the invention:
The purpose of the present invention is to provide a kind of electro-catalysis to produce oxygen NiPS3/ graphene composite catalyst and preparation method thereof, Make full use of NiPS3It the features such as high-specific surface area, satisfactory electrical conductivity of excellent electro-catalysis production oxygen activity and graphene, solves NiPS3Poorly conductive and the non-uniform problem of dispersion, so that electro-catalysis can be realized under lower loading in the composite catalyst It produces the lower take-off potential of oxygen, lesser Tafel slope, high job stability and only needs smaller overpotential that can obtain Higher current density realizes excellent electrocatalysis characteristic.
The technical scheme is that
A kind of electro-catalysis production oxygen NiPS3/ graphene composite catalyst, conductivity are 1.0 × 10-7~1.0 × 105S/m, NiPS3Nanometer sheet content is 5~95wt%, and graphene content is 5~95wt%, and loading is 0.1~1.0mg/cm2, starting electricity Position is 1.46~1.60V, current density 10mA/cm2And 100mA/cm2When overpotential difference 294~350mV and 351~ 450mV, Tafel slope are 42.6~80.0mV/dec.
The electro-catalysis produces oxygen NiPS3/ graphene composite catalyst, it is preferred that NiPS3/ graphene composite catalyst Conductivity is 1.0 × 102~1.3 × 104S/m, NiPS3Nanometer sheet content be 20~60wt%, graphene content be 40~ 80wt%, loading are 0.1~0.4mg/cm2, take-off potential is 1.46~1.50V, current density 10mA/cm2And 100mA/ cm2When overpotential distinguish 294~330mV and 351~430mV, Tafel slope be 42.6~60.0mV/dec.
The electro-catalysis produces oxygen NiPS3The preparation method of/graphene composite catalyst, using vapor transportation method in quartz The cold end of pipe deposits to obtain NiPS3Block, then Tip ultrasound obtains NiPS in water3Nanometer sheet, by NiPS3Nanometer sheet and graphite Alkene is added to ultrasound in Nafion solution, dries standing in mixed dispersion liquid drop coating to electrode, can be obtained NiPS3/ graphite Alkene composite catalyst electrode.
The electro-catalysis produces oxygen NiPS3The preparation method of/graphene composite catalyst, the specific steps are as follows:
(1) vapor-phase transport process synthesizes NiPS3Block: by nickel powder, red phosphorus, sulphur-cake and iodine block according to quality proportioning 634: 334:1032:40 is put into quartz ampoule, in vacuum degree less than 10-3It is packaged under conditions of mbar, it then will be in quartz ampoule 1h 600~1000 DEG C are heated to, cooled to room temperature after reaction 1~30 day takes out product and repeatedly cleans removal residual with acetone Iodine, and be heated to 200~400 DEG C of remaining sulphur of removal under vacuum conditions；
(2) ultrasound prepares NiPS in water3Nanometer sheet: by NiPS3Into the water, Tip ultrasound and high speed centrifugation are handled block Afterwards, it takes out supernatant and obtains NiPS3The stable dispersions of nanometer sheet are filtered by vacuum and obtain NiPS after vacuum and heating drying3Nanometer Piece powder；
(3) preparation electro-catalysis produces oxygen NiPS3/ graphene composite catalyst: by NiPS3Nanometer sheet powder and graphene press one Certainty ratio is added in the Nafion solution that concentration is 0.1~0.3wt% after 0.5~2h of ultrasound, and mixed dispersion liquid drop coating is arrived It stands and dries on electrode, can be obtained NiPS3/ graphene composite catalyst electrode.
The electro-catalysis produces oxygen NiPS3The preparation method of/graphene composite catalyst in step (2), prepares NiPS3It receives The Tip ultrasonic power of rice piece is 95~950W, and Tip ultrasonic time is 1~8h；Prepare NiPS3The centrifugal speed of nanometer sheet is 500 ~10000 rpms, centrifugation time is 10~120min；Obtained NiPS3The Zeta electric potential of nanometer sheet dispersion liquid is -41.2 ~-38.6mV, vacuum drying preparation NiPS3The heating temperature of nanometer sheet powder be 40~80 DEG C, vacuum drying time be 2~ 24h。
The electro-catalysis produces oxygen NiPS3The preparation method of/graphene composite catalyst, NiPS3Nanometer sheet thickness be 3~ 20 layers, lateral dimension is 50~1000nm；The number of plies of graphene film is 3~8 layers, and lateral dimension is at 1~5 μm.
The invention has the advantages and beneficial effects that:
1, the present invention proposes a kind of NiPS3The preparation method of/graphene ULTRASONIC COMPLEX prepares big ruler using vapor transportation method Very little, high quality NiPS3Crystal, Tip ultrasound obtains a small number of layer NiPS in water3The dispersion liquid of nanometer sheet, dispersion liquid can be used directly The electrode catalyst of oxygen is produced in electro-catalysis, ultrasound is mixed with commercial graphene powder after vacuum filtration is dry, obtains NiPS3/ stone Black alkene composite catalyst.
2, the NiPS that the present invention obtains3/ graphene composite material, has both NiPS3Good electro-catalysis produces oxygen activity and stone The advantages such as the high specific surface area of black alkene and excellent electric conductivity are NiPS3It is led with graphene in electro-catalysis and electrochemical energy storage etc. The performance boost of domain application provides may.
3, the NiPS that the present invention obtains3/ graphene composite material keeps size lesser using the size difference of the two NiPS3Nanometer sheet evenly spreads to two surfaces of larger-size graphene, greatly improves NiPS3The dispersibility of nanometer sheet, Be conducive to expose more active sites, the three-dimensional structure of graphene curling is also beneficial to the mass transport process of electrocatalytic reaction, together When, the electronics transfer resistance of the composite material significantly reduces, and electrocatalytic reaction kinetic rate is accelerated.
4, the present invention has the characteristics that easy to operate, at low cost and is easy to structure regulating, it is expected to NiPS be mass produced3/ Graphene composite material.
5, the present invention is adding minimal amount of NiPS3The composite material can be obtained excellent electro-catalysis and produce oxygen when nanometer sheet Performance.Work as NiPS3Nanometer sheet and graphene proportion are 1:1, and NiPS3The loading of nanometer sheet is 0.2mg/cm2When electro-catalysis produce Oxygen performance is best, take-off potential 1.46V, current density 10mA/cm2And 100mA/cm2When overpotential be respectively 294mV And 351mV, Tafel slope 42.6mV/dec, there is very excellent job stability, comprehensive performance is expensive better than traditional Metal oxide (ruthenium-oxide and yttrium oxide).
Detailed description of the invention:
Fig. 1 is NiPS of the present invention3The preparation flow figure of/graphene composite material.
Fig. 2 is NiPS3The morphology characterization of block: (a) optical photograph；(b) electron scanning micrograph.
Fig. 3 is NiPS3The characterization of size of nanometer sheet: (a) photo of dispersion liquid in water；(b) atomic force microscopy； (c-d) the statistical Butut of thickness and size, (c) abscissa Thickness representative thickness (nm), the ordinate Counts in figure It represents and counts, (d) the abscissa Size in figure represents size (nm), ordinate Counts is represented and counted.
Fig. 4 is NiPS3The structural characterization of block and nanometer sheet: (a) X-ray diffraction power spectrum comparison diagram, 2 θ of abscissa are represented The angle of diffraction (degree), ordinate Intensity represent intensity (a.u.)；(b) Raman spectrum comparison diagram, abscissa Raman Shift represents Raman shift (cm-1), ordinate Intensity represents intensity (a.u.).
Fig. 5 is NiPS3The transmission electron microscope of nanometer sheet characterizes: (a) Bright Field Transmission electron micrograph；(b) it selects Area's electron diffraction pattern；(c-f) scanning transmission electron microscope photo (c) and corresponding Ni-K (d), P-K (e), S-K (f) Sweep photo in power spectrum face；(g) high resolution transmission electron microscopy photo.
Fig. 6 is graphene, NiPS3Nanometer sheet and NiPS3The pattern and Raman Characterization of/graphene composite material: (a- C) electron scanning micrograph (a) of graphene, transmission electron microscope photo (b) and Raman spectrum (c)；(d-f)NiPS3 Electron scanning micrograph (d), transmission electron microscope photo (e) and the Raman spectrum (f) of nanometer sheet；(g-i)NiPS3/ Electron scanning micrograph (g), transmission electron microscope photo (h) and the Raman spectrum (i) of graphene composite material.(g), (h) and in (i) figure, abscissa Raman Shift represents Raman shift (cm-1), ordinate Intensity represents intensity (a.u.)。
Fig. 7 is the NiPS of different quality proportion3/ graphene composite material electrocatalysis characteristic test result: (a) electro-catalysis produces Oxygen polarization curve, abscissa Potential vs RHE represent electrode potential (V, relative to reversible hydrogen electrode), ordinate Current density represents current density (mAcm-2)；(b) Tafel slope curve, abscissa Log (Current density(mA·cm-2)) logarithm of current density is represented, ordinate Overpotential represents overpotential (V)；(c) capacitor Curve, abscissa Scan rate are represented sweep speed (mV/s), and ordinate Δ j represents Cyclic voltamogram curve test current potential Difference (the mAcm of midpoint electric current-2)；(d) electrochemical impedance spectroscopy, abscissa ZrealRepresent real impedance (Ω), ordinate-Zim Represent imaginary impedance (Ω).
Fig. 8 is the NiPS of different loadings3The electrochemical property test result of/graphene (mass ratio 1:1) composite material: (a) electro-catalysis produces oxygen polarization curve, and abscissa Potential vs RHE represents electrode potential (V, relative to reversible hydrogen electrode), Ordinate Current density represents current density (mAcm-2)；(b) Tafel slope curve, abscissa Log (Current density(mA·cm-2)) logarithm of current density is represented, ordinate Overpotential represents overpotential (V)。
Fig. 9 is NiPS3The stability test result of/graphene (1:1): (a) 5h stability test i-t curve, abscissa Time represents the time (h), and ordinate Current density represents current density (mAcm-2)；(b) polarization of test front and back Curve comparison figure, abscissa Potential vs RHE represent electrode potential (V, relative to reversible hydrogen electrode), ordinate Current density represents current density (mAcm-2)。
Specific embodiment:
As shown in Figure 1, in the specific implementation process, the present invention proposes that a kind of electro-catalysis produces oxygen NiPS3/ graphene is compound to urge The preparation method of agent deposits to obtain NiPS using vapor transportation method in the cold end of quartz ampoule3Block, then Tip is super in water Sound (using Tip type ultrasonic machine, i.e. ultrasonic cell disruptor) obtains NiPS3Nanometer sheet, by NiPS3Nanometer sheet and graphene are pressed It is added to ultrasound in Nafion (perfluorinated sulfonic resin) solution that concentration is 0.2wt% according to certain mass ratio, mixing is dispersed Drop, which is coated onto stand on electrode, to be dried, and can be obtained NiPS3/ graphene composite catalyst electrode.Specific step is as follows:
(1) vapor-phase transport process synthesizes NiPS3Block: by nickel powder, red phosphorus, sulphur-cake and iodine block according to quality proportioning 634: 334:1032:40 is put into quartz ampoule, in vacuum degree less than 10-3It is packaged under conditions of mbar, it then will be in quartz ampoule 1h 750 DEG C are heated to, cooled to room temperature after reaction 7 days takes out product and repeatedly cleans the remaining iodine of removal with acetone, and true 300 DEG C of remaining sulphur of removal are heated under empty condition.
(2) ultrasound prepares NiPS in water3Nanometer sheet: by NiPS3Into the water, Tip ultrasound and high speed centrifugation are handled block Afterwards, it takes out supernatant and obtains NiPS3The stable dispersions of nanometer sheet.After vacuum filtration and vacuum and heating drying, obtain NiPS3Nanometer sheet powder.
The preparation NiPS3The Tip ultrasonic power of nanometer sheet is 95~950W, and preferred scope is 285~475W；Tip is super The sound time is 1~8h, and preferred scope is 2~6h；Centrifugal speed be 500~10000 rpms, preferred scope be 3000~ 5000 rpms；Centrifugation time is 10~120min, and preferred scope is 30~60min；The NiPS3Nanometer sheet thickness is 3 ~20 layers, preferred scope is 4~8 layers；Lateral dimension is 50~1000nm, and preferred scope is 100~250nm；Graphene film by (referring to Chinese invention patent, patent No. ZL201110282370.5) is made in intercalation-stripping means, and the number of plies of graphene film is 3 ~8 layers, lateral dimension is at 1~5 μm.
(3) preparation electro-catalysis produces oxygen NiPS3/ graphene composite catalyst: by NiPS3Nanometer sheet powder and graphene press one Determine mass ratio to be added in the Nafion solution that concentration is 0.2wt% after 0.5~2h of ultrasound, by mixed dispersion liquid drop coating to electrode Upper standing is dried, and can be obtained NiPS3/ graphene composite catalyst electrode.
The NiPS that the present invention obtains3The conductivity of/graphene composite catalyst is 1.0 × 10-7~1.0 × 105S/m, it is excellent Selecting range is 1.0 × 102~1.3 × 104S/m.The electro-catalysis NiPS3In/graphene composite catalyst, NiPS3Nanometer sheet Content is 5~95wt%, and preferred scope is 20~60wt%；Graphene content be 5~95wt%, preferred scope be 40~ 80wt%；Loading is 0.1~1.0mg/cm2, preferred scope is 0.1~0.4mg/cm2；Take-off potential is 1.46~1.60V, Preferred scope is 1.46~1.50V；Current density is 10mA/cm2And 100mA/cm2When overpotential distinguish 294~330mV and 351~450mV, preferred scope are respectively 294~310mV and 351~430mV；Tafel slope is 42.6~80.0mV/dec, Preferred scope is 42.6~60.0mV/dec.
In the following, the present invention is described in further detail by embodiment and attached drawing.
Embodiment 1
In the present embodiment, by NiPS3Block (Fig. 2) 500mg is put into vial, and 40mL water is added.It is shelled using Tip ultrasound From preparation NiPS3Nanometer sheet (ultrasonic power 380W, ultrasonic time 6h) stands 5000 rpms of centrifugation 30min after 8h, Supernatant is taken out, lilac stable dispersions (Fig. 3 a) are obtained.By supernatant vacuum filtration and 60 DEG C of vacuum drying 12h, obtain NiPS3Nanometer sheet powder.As shown in Figure 3b, from atomic force microscopy as can be seen that the NiPS that removing obtains3Nanometer sheet ruler (average thickness~3.5nm is shown in Fig. 3 c to the significant decrease of very little and thickness；Average-size~140nm, is shown in Fig. 3 d).NiPS3Nanometer sheet 2mg (50wt%) and graphene 2mg (50wt%) is added to ultrasound 60min in the Nafion solution 2mL that concentration is 0.2wt%, Obtain uniform composite dispersion liquid.It is dried being stood in 40 μ L composite diffusion drop-coateds to electrode, can be obtained loading is 0.4mg/cm2NiPS3/ graphene composite catalyst (NiPS3The loading of nanometer sheet is 0.2mg/cm2), conductivity 1.3 ×104S/m。
As shown in the transmission electron microscope characterization in X-ray diffraction power spectrum, Raman spectrum and Fig. 5 in Fig. 4, ultrasound stripping NiPS from after3Nanometer sheet retains higher crystallinity, and crystal quality is higher.
As shown in fig. 6, scanning electron microscope and transmission electron microscope photo can be seen that graphene film size compared with Greatly, in the pleated structure of curling, NiPS3Nanometer chip size it is smaller, be easy to reunite in substrate, with graphene it is compound after, NiPS3 Nanometer sheet can be evenly spread on larger-size graphene film, and dispersibility significantly improves.
As shown in figure 8, electro-catalysis produces oxygen NiPS3The take-off potential of/graphene composite catalyst is 1.46V, current density For 10mA/cm2When overpotential be 294mV, Tafel slope 42.6mV/dec, capacitor 0.454mF/cm2, overpotential is Electronics transfer resistance is 35 Ω when 314mV, is illustrated in NiPS3After middle addition graphene, the kinetic rate that electro-catalysis produces oxygen is aobvious It writes and is promoted.
As shown in figure 9, electro-catalysis produces oxygen NiPS3/ graphene composite catalyst is under conditions of overpotential is 300mV, 5h I-t curve fluctuation it is smaller, and be catalyzed produce oxygen polarization curve be basically unchanged, illustrate NiPS3/ graphene composite material has Very excellent job stability.
Embodiment 2
In the present embodiment, by NiPS3Block (Fig. 2) 500mg is put into vial, and 40mL water is added.It is shelled using Tip ultrasound From preparation NiPS3Nanometer sheet (ultrasonic power 380W, ultrasonic time 6h) stands 5000 rpms of centrifugation 30min after 8h, Supernatant is taken out, lilac stable dispersions (Fig. 3 a) are obtained.By supernatant vacuum filtration and 60 DEG C of vacuum drying 12h, obtain NiPS3Nanometer sheet powder.As shown in Figure 3b, from atomic force microscopy as can be seen that the NiPS that removing obtains3Nanometer sheet ruler (average thickness~3.5nm is shown in Fig. 3 c to the significant decrease of very little and thickness；Average-size~140nm, is shown in Fig. 3 d).NiPS3Nanometer sheet 2mg (50wt%) and graphene 2mg (50wt%) is added to ultrasound 60min in the Nafion solution 2mL that concentration is 0.2wt%, Obtain uniform composite dispersion liquid.It is dried being stood in 20 μ L composite diffusion drop-coateds to electrode, can be obtained loading is 0.2mg/cm2NiPS3/ graphene composite catalyst (NiPS3The loading of nanometer sheet is 0.1mg/cm2)。
As shown in figure 8, electro-catalysis produces oxygen NiPS3The take-off potential of/graphene composite catalyst is 1.46V, current density For 10mA/cm2And 100mA/cm2When overpotential be respectively 300mV and 375mV, Tafel slope 42.4mV/dec.
Embodiment 3
In the present embodiment, by NiPS3Block (Fig. 2) 500mg is put into vial, and 40mL water is added.It is shelled using Tip ultrasound From preparation NiPS3Nanometer sheet (ultrasonic power 380W, ultrasonic time 6h) stands 5000 rpms of centrifugation 30min after 8h, Supernatant is taken out, lilac stable dispersions (Fig. 3 a) are obtained.By supernatant vacuum filtration and 60 DEG C of vacuum drying 12h, obtain NiPS3Nanometer sheet powder.As shown in Figure 3b, from atomic force microscopy as can be seen that the NiPS that removing obtains3Nanometer sheet ruler (average thickness~3.5nm is shown in Fig. 3 c to the significant decrease of very little and thickness；Average-size~140nm, is shown in Fig. 3 d).NiPS3Nanometer sheet 2mg (50wt%) and graphene 2mg (50wt%) is added to ultrasound 60min in the Nafion solution 1mL that concentration is 0.2wt%, Obtain uniform composite dispersion liquid.It is dried being stood in 60 μ L composite diffusion drop-coateds to electrode, can be obtained loading is 0.6mg/cm2NiPS3/ graphene composite catalyst (NiPS3The loading of nanometer sheet is 0.3mg/cm2)。
As shown in figure 8, electro-catalysis produces oxygen NiPS3The take-off potential of/graphene composite catalyst is 1.46V, current density For 10mA/cm2When overpotential be 304mV, Tafel slope 49.9mV/dec.
Embodiment 4
In the present embodiment, by NiPS3Block (Fig. 2) 500mg is put into vial, and 40mL water is added.It is shelled using Tip ultrasound From preparation NiPS3Nanometer sheet (ultrasonic power 380W, ultrasonic time 6h) stands 5000 rpms of centrifugation 30min after 8h, Supernatant is taken out, lilac stable dispersions (Fig. 3 a) are obtained.By supernatant vacuum filtration and 60 DEG C of vacuum drying 12h, obtain NiPS3Nanometer sheet powder.As shown in Figure 3b, from atomic force microscopy as can be seen that the NiPS that removing obtains3Nanometer sheet ruler (average thickness~3.5nm is shown in Fig. 3 c to the significant decrease of very little and thickness；Average-size~140nm, is shown in Fig. 3 d).NiPS3Nanometer sheet 5mg (84.3wt%) and graphene 1mg (16.7wt%) is added to ultrasound in the Nafion solution 3mL that concentration is 0.2wt% 60min obtains uniform composite dispersion liquid.It is dried being stood in 20 μ L composite diffusion drop-coateds to electrode, can be obtained and support Amount is 0.2mg/cm2NiPS3/ graphene composite catalyst.
As shown in fig. 7, electro-catalysis produces oxygen NiPS3The take-off potential of/graphene composite catalyst is 1.48V, current density For 10mA/cm2And 100mA/cm2When overpotential be respectively 324mV and 405mV, Tafel slope 57.6mV/dec.
Embodiment 5
In the present embodiment, by NiPS3Block (Fig. 2) 500mg is put into vial, and 40mL water is added.It is shelled using Tip ultrasound From preparation NiPS3Nanometer sheet (ultrasonic power 380W, ultrasonic time 6h) stands 5000 rpms of centrifugation 30min after 8h, Supernatant is taken out, lilac stable dispersions (Fig. 3 a) are obtained.By supernatant vacuum filtration and 60 DEG C of vacuum drying 12h, obtain NiPS3Nanometer sheet powder.As shown in Figure 3b, from atomic force microscopy as can be seen that the NiPS that removing obtains3Nanometer sheet ruler (average thickness~3.5nm is shown in Fig. 3 c to the significant decrease of very little and thickness；Average-size~140nm, is shown in Fig. 3 d).NiPS3 nanometer sheet 1mg (16.7wt%) and graphene 5mg (84.3wt%) is added to ultrasound in the Nafion solution 3mL that concentration is 0.2wt% 60min obtains uniform composite dispersion liquid.It is dried being stood in 20 μ L composite diffusion drop-coateds to electrode, can be obtained and support Amount is 0.2mg/cm2NiPS3/ graphene composite catalyst.
As shown in fig. 7, electro-catalysis produces oxygen NiPS3The take-off potential of/graphene composite catalyst is 1.47V, current density For 10mA/cm2And 100mA/cm2When overpotential distinguish 319mV and 406mV, Tafel slope 46.6mV/dec.
Embodiment 6
In the present embodiment, by NiPS3Block (Fig. 2) 500mg is put into vial, and 40mL water is added.It is shelled using Tip ultrasound From preparation NiPS3Nanometer sheet (ultrasonic power 380W, ultrasonic time 6h) stands 5000 rpms of centrifugation 30min after 8h, Supernatant is taken out, lilac stable dispersions (Fig. 3 a) are obtained.By supernatant vacuum filtration and 60 DEG C of vacuum drying 12h, obtain NiPS3Nanometer sheet powder.As shown in Figure 3b, from atomic force microscopy as can be seen that the NiPS that removing obtains3Nanometer sheet ruler (average thickness~3.5nm is shown in Fig. 3 c to the significant decrease of very little and thickness；Average-size~140nm, is shown in Fig. 3 d).NiPS3Nanometer sheet 5mg (90.9wt%) and graphene 0.5mg (9.1wt%), which is added in the Nafion solution 2.75mL that concentration is 0.2wt%, to be surpassed Sound 60min obtains uniform composite dispersion liquid.It is dried being stood in 20 μ L composite diffusion drop-coateds to electrode, can be obtained load Carrying capacity is 0.2mg/cm2NiPS3/ graphene composite catalyst.
As shown in fig. 7, electro-catalysis produces oxygen NiPS3The take-off potential of/graphene composite catalyst is 1.48V, current density For 10mA/cm2And 100mA/cm2When overpotential distinguish 328mV and 429mV, Tafel slope 51.3mV/dec.
Embodiment 7
In the present embodiment, by NiPS3Block (Fig. 2) 500mg is put into vial, and 40mL water is added.It is shelled using Tip ultrasound From preparation NiPS3Nanometer sheet (ultrasonic power 380W, ultrasonic time 6h) stands 5000 rpms of centrifugation 30min after 8h, Supernatant is taken out, lilac stable dispersions (Fig. 3 a) are obtained.By supernatant vacuum filtration and 60 DEG C of vacuum drying 12h, obtain NiPS3Nanometer sheet powder.As shown in Figure 3b, from atomic force microscopy as can be seen that the NiPS that removing obtains3Nanometer sheet ruler (average thickness~3.5nm is shown in Fig. 3 c to the significant decrease of very little and thickness；Average-size~140nm, is shown in Fig. 3 d).NiPS3Nanometer sheet 0.5mg (9.1wt%) and graphene 5mg (90.9wt%), which is added in the Nafion solution 2.75mL that concentration is 0.2wt%, to be surpassed Sound 60min obtains uniform composite dispersion liquid.It is dried being stood in 20 μ L composite diffusion drop-coateds to electrode, can be obtained load Carrying capacity is 0.2mg/cm2NiPS3/ graphene composite catalyst.
As shown in fig. 7, electro-catalysis produces oxygen NiPS3The take-off potential of/graphene composite catalyst is 1.47V, current density For 10mA/cm2And 100mA/cm2When overpotential be respectively 322mV and 415mV, Tafel slope 47.6mV/dec.
Embodiment 8
In the present embodiment, by NiPS3Block (Fig. 2) 500mg is put into vial, and 40mL water is added.It is shelled using Tip ultrasound From preparation NiPS3Nanometer sheet (ultrasonic power 380W, ultrasonic time 6h) stands 5000 rpms of centrifugation 30min after 8h, Supernatant is taken out, lilac stable dispersions (Fig. 3 a) are obtained.By supernatant vacuum filtration and 60 DEG C of vacuum drying 12h, obtain NiPS3Nanometer sheet powder.As shown in Figure 3b, from atomic force microscopy as can be seen that the NiPS that removing obtains3Nanometer sheet ruler (average thickness~3.5nm is shown in Fig. 3 c to the significant decrease of very little and thickness；Average-size~140nm, is shown in Fig. 3 d).NiPS3Nanometer sheet 2mg (100wt%) and graphene 0mg (0wt%) is added to ultrasound 60min in the Nafion solution 1mL that concentration is 0.2wt%, Obtain uniform composite dispersion liquid.It is dried being stood in 20 μ L composite diffusion drop-coateds to electrode, can be obtained loading is 0.2mg/cm2NiPS3/ graphene composite catalyst, conductivity are 1.0 × 10-7S/m。
As shown in fig. 7, electro-catalysis produces oxygen NiPS3The take-off potential of/graphene composite catalyst is 1.48V, current density For 10mA/cm2When overpotential be 343mV, Tafel slope 58.9mV/dec, capacitor 0.141mF/cm2, overpotential is Electronics transfer resistance is 191 Ω when 314mV.
Electrocatalysis characteristic test:
Double potentiostat CHI760D or the Autolab electrochemical workstation produced using Shanghai Chen Hua instrument company is used Three electrode test systems, composite material dispersant liquid drop are coated on glass-carbon electrode as working electrode, and platinum electrode is used as to electrode, is satisfied With calomel electrode as reference electrode, the KOH solution of molar concentration 1M is electrolyte.Composite material loading be 0.1~ 1.0mg/cm2, test voltage is 1.2V to 1.7V (relative to reversible hydrogen electrode), and test content includes that cyclic voltammetry (CV) is surveyed Examination, linear sweep voltammetry (SLV) test, impedance spectrum test, stability test etc..
The above results show that NiPS is prepared by techniques such as vapor transportation methods in the present invention3Nanometer sheet, and and graphene It is compound to obtain NiPS3/ graphene composite material.The composite material does not realize NiPS merely with the high specific surface area of graphene3Nanometer Piece it is evenly dispersed；Meanwhile in conjunction with NiPS3Good electro-catalysis produces oxygen activity and the excellent electric conductivity of graphene, realizes and exists It can be obtained electro-catalysis under lower loading and produce the lower take-off potential of oxygen, Tafel slope, high job stability and only Need smaller overpotential that can obtain higher current density.Operation of the present invention is easy, yield is high, is easy to carry out structure regulating, thus For NiPS3And graphene is catalyzed in high-performance electric and the application in the fields such as energy storage device lays the foundation.

Claims (6)

1. a kind of electro-catalysis produces oxygen NiPS3/ graphene composite catalyst, it is characterised in that: NiPS3/ graphene composite catalyst Conductivity is 1.0 × 10-7~1.0 × 105S/m, NiPS3Nanometer sheet content be 5~95wt%, graphene content be 5~ 95wt%, loading are 0.1~1.0mg/cm2, take-off potential is 1.46~1.60V, current density 10mA/cm2And 100mA/ cm2When overpotential distinguish 294~350mV and 351~450mV, Tafel slope be 42.6~80.0mV/dec.
2. electro-catalysis described in accordance with the claim 1 produces oxygen NiPS3/ graphene composite catalyst, it is characterised in that: it is preferred, NiPS3The conductivity of/graphene composite catalyst is 1.0 × 102~1.3 × 104S/m, NiPS3Nanometer sheet content be 20~ 60wt%, graphene content are 40~80wt%, and loading is 0.1~0.4mg/cm2, take-off potential is 1.46~1.50V, electricity Current density is 10mA/cm2And 100mA/cm2When overpotential distinguish 294~330mV and 351~430mV, Tafel slope is 42.6~60.0mV/dec.
3. a kind of electro-catalysis of any of claims 1 or 2 produces oxygen NiPS3The preparation method of/graphene composite catalyst, feature It is: deposits to obtain NiPS in the cold end of quartz ampoule using vapor transportation method3Block, then Tip ultrasound obtains NiPS in water3 Nanometer sheet, by NiPS3Nanometer sheet and graphene are added to ultrasound in Nafion solution, will be quiet in mixed dispersion liquid drop coating to electrode It sets and dries, is i.e. acquisition NiPS3/ graphene composite catalyst electrode.
4. electro-catalysis described in accordance with the claim 3 produces oxygen NiPS3The preparation method of/graphene composite catalyst, feature exist In, the specific steps are as follows:
(1) vapor transportation method synthesizes NiPS3Block: by nickel powder, red phosphorus, sulphur-cake and iodine block according to quality proportioning 634:334:1032: 40 are put into quartz ampoule, in vacuum degree less than 10-3It is packaged under conditions of mbar, then will be heated to 600 in quartz ampoule 1h ~1000 DEG C, cooled to room temperature after reaction 1~30 day takes out product with acetone and cleans the remaining iodine of removal, and in vacuum Under the conditions of be heated to 200~400 DEG C of remaining sulphur of removal；
(2) ultrasound prepares NiPS in water3Nanometer sheet: by NiPS3Block into the water, Tip ultrasound and high speed centrifugation processing after, It takes out supernatant and obtains NiPS3The stable dispersions of nanometer sheet are filtered by vacuum and obtain NiPS after vacuum and heating drying3Nanometer sheet Powder；
(3) preparation electro-catalysis produces oxygen NiPS3/ graphene composite catalyst: by NiPS3Nanometer sheet powder and graphene are added to dense Degree is to dry in the Nafion solution of 0.1~0.3wt% after 0.5~2h of ultrasound by standing in mixed dispersion liquid drop coating to electrode, Obtain NiPS3/ graphene composite catalyst electrode.
5. electro-catalysis produces oxygen NiPS according to claim 43The preparation method of/graphene composite catalyst, feature exist In, in step (2), preparation NiPS3The Tip ultrasonic power of nanometer sheet is 95~950W, and Tip ultrasonic time is 1~8h；Preparation NiPS3The centrifugal speed of nanometer sheet is 500~10000 rpms, and centrifugation time is 10~120min；Obtained NiPS3Nanometer The Zeta electric potential of piece dispersion liquid is -41.2~-38.6mV, vacuum drying preparation NiPS3The heating temperature of nanometer sheet powder is 40 ~80 DEG C, the time be 2~for 24 hours.
6. producing oxygen NiPS according to electro-catalysis described in claim 3 or 43The preparation method of/graphene composite catalyst, feature It is: NiPS3Nanometer sheet thickness is 3~20 layers, and lateral dimension is 50~1000nm；The number of plies of graphene film is 3~8 layers, horizontal To size at 1~5 μm.
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CN114836766A (en) * 2022-04-12 2022-08-02 西安交通大学 MoS 2 /NiPS 3 Composite heterostructure nanosheet electrocatalyst and preparation method and application thereof
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112551599A (en) * 2020-12-10 2021-03-26 西安交通大学深圳研究院 Nickel sulfate phosphate nanosheet/graphene composite material and preparation method thereof
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CN114836766A (en) * 2022-04-12 2022-08-02 西安交通大学 MoS 2 /NiPS 3 Composite heterostructure nanosheet electrocatalyst and preparation method and application thereof
CN114836766B (en) * 2022-04-12 2024-04-02 西安交通大学 MoS (MoS) 2 /NiPS 3 Composite heterostructure nanosheet electrocatalyst and preparation method and application thereof
CN114990580A (en) * 2022-07-15 2022-09-02 桂林电子科技大学 Composite heterostructure nanosheet, preparation method and application
CN114990580B (en) * 2022-07-15 2023-06-02 桂林电子科技大学 Composite heterostructure nanosheet, preparation method and application

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