CN109183058A - A kind of construction method of the catalytic hydrogen evolution electrode of abundant exposed molybdenum disulfide active sites - Google Patents
A kind of construction method of the catalytic hydrogen evolution electrode of abundant exposed molybdenum disulfide active sites Download PDFInfo
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- CN109183058A CN109183058A CN201811060369.6A CN201811060369A CN109183058A CN 109183058 A CN109183058 A CN 109183058A CN 201811060369 A CN201811060369 A CN 201811060369A CN 109183058 A CN109183058 A CN 109183058A
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Abstract
The invention belongs to two-dimensional material preparation and catalytic hydrogen evolution technical fields, and in particular to a kind of construction method of the catalytic hydrogen evolution electrode of abundant exposed molybdenum disulfide active sites.For the low problem of existing molybdenum disulfide nano thin slice catalytic hydrogen evolution active site abundance, technological core of the invention includes the following: [1] utilizes the immobilized molybdenum disulfide of print process, constructs three-dimensional catalytic hydrogen-precipitating electrode；[2] surfactant polyvinylpyrrolidone, up-stripping molybdenum disulfide are mixed, and prevents the reaggregation of molybdenum disulfide nano thin slice；[3] it mixes redox graphene and provides anchor point for the dispersion of molybdenum disulfide nano thin slice, further prevent the stacking of molybdenum disulfide nano thin slice；[4] select the carrier with high surface roughness as electrode basement.Catalytic hydrogen evolution reaction of the present invention suitable for acid solution under room temperature.
Description
Technical field
The invention belongs to two-dimensional material preparation and electrocatalytic hydrogen evolution technical fields, and in particular to a kind of abundant two sulphur of exposure
Change the construction method of the catalytic hydrogen evolution electrode of molybdenum active sites.
Background technique
Traditional fossil fuel is non-renewable due to serious problem of environmental pollution and fuel, just gradually novel
Sustainable energy replaces.A kind of energy carrier of the Hydrogen Energy as high-efficiency cleaning is taken as the ideal replacer of conventional fossil fuel.
However inefficient and production technology the complexity of production of hydrogen all restricts the development of hydrogen energy source.
Water electrolysis hydrogen production is considered as the sustainable important channel for obtaining hydrogen, and the design of efficient electrocatalytic hydrogen evolution material is
It is related to the key that can this technology be realized.Currently, the core missions in water electrolysis hydrogen production field be solve high hydrogen production efficiency with
Contradiction between low catalysis cost, thus the catalyst for preparing hydrogen and related process of development efficiently, economic, green, to replace resource
Metallic platinum catalyst that is limited, involving great expense realizes the low cost conversion of energy.
As a type grapheme two-dimension material, molybdenum disulfide has the hydrogen adsorption free energy similar to metal platinum, can
It is stabilized in strongly acidic solution and resourceful, is expected to replace conventional precious metal liberation of hydrogen material.Research (Anders B L,
Soren K,Soren D,et al.Molybdenum sulfides-efficient and viable materials for
electro-and photoelectrocatalytic hydrogen evolution,Energy&Environmental
Science, 2012,5:5577) show that the active site of molybdenum disulfide is located atThe edge of crystal face, therefore increase
The edge exposed area of molybdenum disulfide becomes an important channel for promoting its catalytic hydrogen evolution performance.Its active site at present
Exposure there is also problems, be mainly manifested in: (1) the class graphene sheet layer size of molybdenum disulfide is larger, and pole is unfavorable for it
The exposure in edge active site；(2) easily occur to accumulate again due to van der Waals interaction between molybdenum disulfide nano sheet layer, thus
Reduce the abundance in hydrogen evolution activity site；(3) the immobilized mode of molybdenum disulfide is single, can expose the space of more active sites
Structure design means are deficient.
Summary of the invention
For existing molybdenum disulfide lamella size, big, piece interlayer easily accumulate and can expose the spaces of more active sites and ties
Structure design means scarcity problem, the present invention provide a kind of side of constructing of the catalytic hydrogen evolution electrode of abundant exposed molybdenum disulfide active sites
Method.Its object is to: the removing of body material molybdenum disulfide is effectively facilitated by the way that surfactant polyvinylpyrrolidone is added, and is reduced
The radial dimension of lamella, and prevent the stacking of molybdenum disulfide nano sheet layer；Redox graphene is added, lamella curing is provided
The dispersion anchor point of molybdenum further prevents the accumulation of molybdenum disulfide nano sheet layer；Using the electrode basement with high surface roughness,
Effectively increase electrode specific surface area, to improve the quantity of active site；Progress can be facilitated using digital printing technology
Patterned advantage forms the three-dimensional graph structure of catalytic hydrogen evolution active material, further increases the sudden and violent of active site
Reveal quantity.
The technical solution adopted by the invention is as follows:
A kind of construction method of the catalytic hydrogen evolution electrode of abundant exposed molybdenum disulfide active sites, which is characterized in that including such as
Lower step:
[1] preparation includes the dispersion liquid of molybdenum disulfide nano thin slice；
[2] it using the dispersion liquid comprising molybdenum disulfide nano thin slice of step [1] preparation as printing ink, is printed using ink-jet
Brush method forms stereo graphic pattern molybdenum-disulfide radical catalytic hydrogen evolution electrode in electrode basement.
Printed electronics for pattern process route, realize the Direct precipitation of functional material, relatively with " addition process "
In the tradition " etching subtractive process " of microelectronic field, there is production technology simplicity, raw material to be lost, and small, equipment investment is few, and can
The advantages of realizing large area, low cost, mass production.Ink-jet printing technology is one of number non-contact, without plate-making
Word printing technology.Ink-jet printing technology is converted in the preparation of catalytic hydrogen evolution electrode by the technical program, so that as electro-catalysis
The molybdenum disulfide nano thin slice of agent forms three-dimensional pattern in electrode basement.Effectively increase catalytic hydrogen evolution active site
Exposure quantity, so that the catalytic hydrogen evolution electrode that this method is prepared has better catalytic activity.
Preferably, include molybdenum disulfide nano thin slice dispersion liquid the preparation method comprises the following steps:
[1-1] obtains the suspension comprising molybdenum disulfide nano thin slice using liquid phase ultrasound stripping method, super in the liquid phase
It is added with surfactant in removing solvent in sound stripping method and accumulates inhibitor again；
The suspension comprising molybdenum disulfide nano thin slice that step [1-1] obtains is centrifuged in [1-2], takes three points
Two at supernatant obtain molybdenum-disulfide radical nano flake dispersion liquid；
It is further preferred that surfactant is polyvinylpyrrolidone.
Polyvinylpyrrolidone, which is added, can effectively facilitate the removing of body material molybdenum disulfide, reduce the radial dimension of lamella, and
The stacking again of molybdenum disulfide nano sheet layer is prevented, to improve the quantity of the catalytic hydrogen evolution active site of the electrode finally prepared.
It is further preferred that the polyethylene in removing solvent is added in step [1-1] the liquid phase ultrasound stripping process
The mass ratio of pyrrolidones and molybdenum disulfide is 0.15~0.25:1.
It is further preferred that accumulation inhibitor is redox graphene again.
Redox graphene is added, it is possible to provide the dispersion anchor point of lamella molybdenum disulfide further prevents molybdenum disulfide from receiving
The accumulation of rice lamella, to improve the active site exposure quantity of catalytic hydrogen evolution electrode made of molybdenum disulfide nano thin slice.
It is further preferred that the oxygen reduction in removing solvent is added in step [1-1] the liquid phase ultrasound stripping process
The mass ratio of graphite alkene and molybdenum disulfide is 0.05~0.15:1.
Preferably, step [2] electrode basement be that surface is covered with conductive film, rigidity that surface roughness is big or
Flexible substrate.
Preferably, the process of stereo graphic pattern molybdenum-disulfide radical catalytic hydrogen evolution electrode is formed in step [2] are as follows: first with plane
Figure spray printing is multiple, then multiple with rectangular convolution line or concentric circles spray printing.
Preferably, the process of stereo graphic pattern molybdenum-disulfide radical catalytic hydrogen evolution electrode is formed in step [2] are as follows: first with plane
Figure spray printing 10 times, then with rectangular convolution line or concentric circles spray printing 10-20 times.
Compared with prior art, the invention has the benefit that
(1) it can be facilitated using digital printing technology and carry out patterned advantage, form the three of catalytic hydrogen evolution active material
Stereo graphics structure is tieed up, the exposure quantity of catalytic hydrogen evolution active site is further increased；(2) surfactant polyethylene is added
Pyrrolidones can effectively facilitate the removing of body material molybdenum disulfide, reduce the radial dimension of lamella, and prevent molybdenum disulfide nano sheet
The stacking again of layer, to improve the quantity of catalytic hydrogen evolution active site；(3) it is added and accumulates inhibitor redox graphene again,
The dispersion anchor point of lamella molybdenum disulfide is provided, the accumulation of molybdenum disulfide nano sheet layer is further prevented, improves catalytic hydrogen evolution activity
The exposure quantity in site；(4) electrode basement with high surface roughness can effectively increase specific surface area, to improve catalysis analysis
The exposure quantity in hydrogen activity site；(5) catalytic hydrogen evolution electrode prepared by the present invention has very high catalytic hydrogen evolution activity；(6) originally
The technical solution of invention is highly susceptible to implementing, and preparation cost is low, and can realize and be prepared on a large scale.
Detailed description of the invention
Examples of the present invention will be described by way of reference to the accompanying drawings, in which:
Fig. 1 is the optical microscope photograph of three-dimensional catalytic hydrogen-precipitating electrode on Teslin paper base that the embodiment of the present invention 1 obtains；
Fig. 2 is that the linear sweep voltammetry of three-dimensional catalytic hydrogen-precipitating electrode on Teslin paper base that the embodiment of the present invention 1 obtains is bent
Line chart and Tafel curve graph；
Fig. 3 is that the linear sweep voltammetry of plane catalytic hydrogen evolution electrode on Teslin paper base that the embodiment of the present invention 2 obtains is bent
Line chart and Tafel curve graph；
Fig. 4 is that the linear sweep voltammetry of plane catalytic hydrogen evolution electrode on Teslin paper base that comparative example 1 of the present invention obtains is bent
Line chart and Tafel curve graph；
Fig. 5 is that the linear sweep voltammetry of three-dimensional catalytic hydrogen-precipitating electrode on Teslin paper base that comparative example 2 of the present invention obtains is bent
Line chart and Tafel curve graph；
Fig. 6 is that the linear sweep voltammetry of three-dimensional catalytic hydrogen-precipitating electrode on Teslin paper base that comparative example 3 of the present invention obtains is bent
Line chart and Tafel curve graph；
Fig. 7 be molybdenum disulfide (a) in comparative example 2 of the present invention, molybdenum disulfide/polyvinylpyrrolidone (b) in comparative example 3,
Molybdenum disulfide/polyvinylpyrrolidone/redox graphene (c) SEM figure in embodiment 1；
Fig. 8 is molybdenum disulfide in comparative example 2 of the present invention, molybdenum disulfide/polyvinylpyrrolidone, embodiment 1 in comparative example 3
Middle molybdenum disulfide/polyvinylpyrrolidone/redox graphene UV-visible absorption spectrum；
Fig. 9 is the linear sweep voltammetry of three-dimensional catalytic hydrogen-precipitating electrode on polyimide substrate that comparative example 4 of the present invention obtains
Curve graph and Tafel curve graph.
Specific embodiment
All features disclosed in this specification or disclosed all methods or in the process the step of, in addition to mutually exclusive
Feature and/or step other than, can combine in any way.
A kind of construction method of the catalytic hydrogen evolution electrode of abundant exposed molybdenum disulfide active sites, includes the following steps:
[1] preparation includes the dispersion liquid of molybdenum disulfide nano thin slice；
[2] it using the dispersion liquid comprising molybdenum disulfide nano thin slice of step [1] preparation as printing ink, is printed using ink-jet
Brush method forms stereo graphic pattern molybdenum-disulfide radical catalytic hydrogen evolution electrode in electrode basement.
Preferably, include molybdenum disulfide nano thin slice dispersion liquid the preparation method comprises the following steps:
[1-1] obtains the suspension comprising molybdenum disulfide nano thin slice using liquid phase ultrasound stripping method, super in the liquid phase
Surfactant is added in removing solvent in sound stripping method and accumulates inhibitor again；
The suspension comprising molybdenum disulfide nano thin slice that step [1-1] obtains is centrifuged in [1-2], takes three points
Two at supernatant obtain molybdenum-disulfide radical nano flake dispersion liquid；
It is further preferred that surfactant is polyvinylpyrrolidone.
It is further preferred that the polyethylene in removing solvent is added in step [1-1] the liquid phase ultrasound stripping process
The mass ratio of pyrrolidones and molybdenum disulfide is 0.15~0.25:1.
It is further preferred that accumulation inhibitor is redox graphene again.
It is further preferred that the oxygen reduction in removing solvent is added in step [1-1] the liquid phase ultrasound stripping process
The mass ratio of graphite alkene and molybdenum disulfide is 0.05~0.15:1.
Preferably, step [2] electrode basement be that surface is covered with conductive film, rigidity that surface roughness is big or
Flexible substrate.
Preferably, the process of stereo graphic pattern molybdenum-disulfide radical catalytic hydrogen evolution electrode is formed in step [2] are as follows: first with plane
Figure spray printing is multiple, then multiple with rectangular convolution line pattern spray printing.
Preferably, the process of stereo graphic pattern molybdenum-disulfide radical catalytic hydrogen evolution electrode is formed in step [2] are as follows: first with plane
Figure spray printing 10 times, then with rectangular convolution line or concentric circles spray printing 10-20 times.
With reference to the accompanying drawing and example, further technical solution of the present invention is illustrated.
Embodiment 1
10mL ethyl alcohol is mixed in beaker with 10mL deionized water, the polyvinylpyrrolidone of 40mg is added, so
After weigh molybdenum disulphide powder powder stock 200mg and redox graphene powder raw material 20mg and be scattered in mixed solution,
It is configured to molybdenum disulfide suspension.Molybdenum disulfide suspension is transferred to progress liquid phase removing in ultrasonic pond, and to liquid phase ultrasound
Treated molybdenum disulfide suspension carries out centrifugal treating, and the supernatant at centrifuge tube 2/3rds is taken to obtain molybdenum disulfide/poly-
Vinylpyrrolidone/redox graphene dispersion liquid (i.e. molybdenum disulfide nano thin slice dispersion liquid), as catalytic hydrogen evolution activity
Material.
Molybdenum disulfide/polyvinylpyrrolidone/redox graphene spray printing is covered in surface using ink jet printing method
Have on the Teslin paper base of copper conductive film.It is as described below that it patterns configuration: first with planar graph (area 0.5*0.5cm2)
Spray printing 10 times, then with rectangular convolution line pattern spray printing 10 times, obtain the catalytic hydrogen evolution working electrode with 3 D stereo configuration.
Linear sweep voltammetry characteristic present is carried out to the working electrode, characterization uses three-electrode system, and electrolyte used is 0.5M sulfuric acid
Solution, reference electrode used are silver/silver chloride electrode, and used is platinum plate electrode to electrode.
Fig. 1 is the light micrograph of three-dimensional catalytic hydrogen-precipitating electrode on Teslin paper base that the embodiment of the present invention obtains.From
Fig. 1 can obviously observe catalytic active substance and be formed by 3-d modelling, which is conducive to expose more catalytic active sites
Point.
Fig. 2 is the linear sweep voltammetry curve of three-dimensional catalytic hydrogen-precipitating electrode on Teslin paper base that the embodiment of the present invention obtains
Figure and Tafel curve graph.As shown in Figure 2, in embodiment molybdenum-disulfide radical catalytic hydrogen evolution electrode current density be 10mA/cm2
When overpotential of hydrogen evolution be 51mV, Tafel slope is 55mV/dec, illustrates on the Teslin paper base that three-dimensional catalytic hydrogen-precipitating electrode has
There is splendid catalytic hydrogen evolution performance.
Embodiment 2
10mL ethyl alcohol is mixed in beaker with 10mL deionized water, the polyvinylpyrrolidone of 40mg is added, so
After weigh molybdenum disulphide powder powder stock 200mg and redox graphene powder raw material 20mg and be scattered in mixed solution,
It is configured to molybdenum disulfide suspension.Molybdenum disulfide suspension is transferred to progress liquid phase removing in ultrasonic pond, and to liquid phase ultrasound
Treated molybdenum disulfide suspension carries out centrifugal treating, and the supernatant at centrifuge tube 2/3rds is taken to obtain molybdenum disulfide/poly-
Vinylpyrrolidone/redox graphene dispersion liquid (i.e. molybdenum disulfide nano thin slice dispersion liquid), as catalytic hydrogen evolution activity
Material.
Molybdenum disulfide/polyvinylpyrrolidone/redox graphene spray printing is covered in surface using ink jet printing method
Have on the Teslin paper base of copper conductive film.It is as described below that it patterns configuration: first with planar graph (area 0.5*0.5cm2)
Spray printing 10 times, then with concentric circles spray printing 10 times, obtain the catalytic hydrogen evolution working electrode with 3 D stereo configuration.To this
Working electrode carries out linear sweep voltammetry characteristic present, and characterization uses three-electrode system, and electrolyte used is 0.5M sulfuric acid solution,
Reference electrode used is silver/silver chloride electrode, and used is platinum plate electrode to electrode.
Fig. 3 is the linear sweep voltammetry curve of three-dimensional catalytic hydrogen-precipitating electrode on Teslin paper base that the embodiment of the present invention obtains
Figure and Tafel curve graph.From the figure 3, it may be seen that in embodiment molybdenum-disulfide radical catalytic hydrogen evolution electrode current density be 10mA/cm2
When overpotential of hydrogen evolution be 54mV, Tafel slope be 56mV/dec.
Comparative example 1
10mL ethyl alcohol is mixed in beaker with 10mL deionized water, the polyvinylpyrrolidone of 40mg is added, so
After weigh molybdenum disulphide powder powder stock 200mg and redox graphene powder raw material 20mg and be scattered in mixed solution,
It is configured to molybdenum disulfide suspension.Molybdenum disulfide suspension is transferred to progress liquid phase removing in ultrasonic pond, and to liquid phase ultrasound
Treated molybdenum disulfide suspension carries out centrifugal treating, and the supernatant at centrifuge tube 2/3rds is taken to obtain molybdenum disulfide/poly-
Vinylpyrrolidone/redox graphene dispersion liquid, as catalytic hydrogen evolution active material.
Using ink jet printing method by molybdenum disulfide/polyvinylpyrrolidone/redox graphene composite material spray printing in
Surface is covered on the Teslin paper base of copper conductive film.When spray printing, with planar graph (area 0.5*0.5cm2) repeat spray printing
20 times, obtain catalytic hydrogen evolution plane working electrode.Linear sweep voltammetry characteristic present is carried out to the working electrode, characterization uses three
Electrode system, electrolyte used are 0.5M sulfuric acid solution, and reference electrode used is silver/silver chloride electrode, and used is platinum to electrode
Plate electrode.
Fig. 4 is that the linear sweep voltammetry of catalytic hydrogen evolution plane electrode on Teslin paper base that comparative example 1 of the present invention obtains is bent
Line chart and Tafel curve graph.As shown in Figure 4, the Teslin paper base catalytic hydrogen evolution plane electrode in comparative example 1 is in current density
For 10mA/cm2When overpotential of hydrogen evolution be 56mV, Tafel slope be 57mV/dec.
By embodiment 1, embodiment 2 and comparative example 1 it is found that being carried out using ink jet printing method to catalytic hydrogen evolution material three-dimensional vertical
Body configuration can effectively expose more catalytic hydrogen evolution active sites in unit area, to promote the catalytic hydrogen evolution of electrode
Energy.
Comparative example 2
10mL ethyl alcohol is mixed in beaker with 10mL deionized water, then weighs molybdenum disulphide powder powder stock
200mg is simultaneously scattered in mixed solution, is configured to molybdenum disulfide suspension.By molybdenum disulfide suspension be transferred in ultrasonic pond into
The removing of row liquid phase, and centrifugal treating is carried out to the molybdenum disulfide suspension after liquid phase ultrasonic treatment, it takes at centrifuge tube 2/3rds
Supernatant obtain molybdenum disulfide dispersion liquid, as catalytic hydrogen evolution active material.
Molybdenum disulfide catalytic hydrogen evolution material spray printing is covered with copper conductive film in surface using ink jet printing method
On Teslin paper base.It is as described below that it patterns configuration: first with planar graph (area 0.5*0.5cm2) spray printing 10 times, then with
Rectangular convolution line pattern spray printing 10 times, obtains the catalytic hydrogen evolution working electrode with 3 D stereo configuration.To the working electrode into
Row linear scan C-V characteristic characterization, characterization use three-electrode system, and electrolyte used is 0.5M sulfuric acid solution, reference electricity used
Extremely silver/silver chloride electrode, used is platinum plate electrode to electrode.
Fig. 5 is that the linear sweep voltammetry of three-dimensional catalytic hydrogen-precipitating electrode on Teslin paper base that comparative example 2 of the present invention obtains is bent
Line chart and Tafel curve graph.As shown in Figure 5, the Teslin paper base three-dimensional catalytic hydrogen-precipitating electrode in comparative example 2 is in current density
For 10mA/cm2When overpotential of hydrogen evolution be 93mV, Tafel slope be 77mV/dec.
Comparative example 3
10mL ethyl alcohol is mixed in beaker with 10mL deionized water, then weighs molybdenum disulphide powder powder stock
200mg and polyvinylpyrrolidonepowder powder 40mg is simultaneously scattered in mixed solution, is configured to molybdenum disulfide suspension.By two sulphur
Change molybdenum suspension and be transferred in ultrasonic pond progress liquid phase removing, and to the molybdenum disulfide suspension after liquid phase ultrasonic treatment carry out from
Heart processing, takes the supernatant at centrifuge tube 2/3rds to obtain molybdenum disulfide/polyvinylpyrrolidone dispersion liquid, as catalysis analysis
Hydrogen activity material.
Molybdenum disulfide/polyethylene ketopyrrolidine composite material spray printing is covered with copper conduction in surface using ink jet printing method
On the Teslin paper base of film.It is as described below that it patterns configuration: first with planar graph (area 0.5*0.5cm2) spray printing 10 times,
Then with rectangular convolution line pattern spray printing 10 times, the catalytic hydrogen evolution working electrode with 3 D stereo configuration is obtained.To the work
Electrode carries out linear sweep voltammetry characteristic present, and characterization uses three-electrode system, and electrolyte used is 0.5M sulfuric acid solution, used
Reference electrode is silver/silver chloride electrode, and used is platinum plate electrode to electrode.
Fig. 6 is that the linear sweep voltammetry of three-dimensional catalytic hydrogen-precipitating electrode on Teslin paper base that comparative example 3 of the present invention obtains is bent
Line chart and Tafel curve graph.It will be appreciated from fig. 6 that the Teslin paper base catalytic hydrogen evolution three-diemsnional electrode in comparative example 3 is in current density
For 10mA/cm2When overpotential of hydrogen evolution be 63mV, Tafel slope be 56mV/dec.
Fig. 7 is molybdenum disulfide (a) in comparative example 2, molybdenum disulfide/polyvinylpyrrolidone (b), embodiment 1 in comparative example 3
Middle molybdenum disulfide/polyvinylpyrrolidone/redox graphene (c) SEM figure.It can be seen from the figure that polyethylene is added
After pyrrolidones, the radial dimension of molybdenum disulfide substantially reduces；After redox graphene is added, redox graphene is three-dimensional
It is scattered in molybdenum disulfide, this can prevent the accumulation of thin layer molybdenum disulfide.
Fig. 8 is molybdenum disulfide in comparative example 2, molybdenum disulfide/polyvinylpyrrolidone in comparative example 3, two sulphur in embodiment 1
Change molybdenum/polyvinylpyrrolidone/redox graphene UV-visible absorption spectrum, it can be seen from the figure that with poly-
The concentration of the addition of vinylpyrrolidone and redox graphene, molybdenum disulfide is sequentially increased, and is computed comparative example 2, comparison
The concentration of molybdenum disulfide is followed successively by 0.15,0.41,0.71mg/mL in example 3, embodiment 1.This further demonstrates polyvinyl pyrroles
The up-stripping effect of alkanone and the accumulation inhibiting effect again of redox graphene.
By comparative example 2 and comparative example 3 it is found that the incorporation of polyvinylpyrrolidone effectively improves the catalysis analysis of molybdenum disulfide
Hydrogen performance；By embodiment 1 and comparative example 3 it is found that the incorporation of redox graphene further improves the catalysis of molybdenum disulfide
Hydrogen Evolution Performance.
Comparative example 4
10mL ethyl alcohol is mixed in beaker with 10mL deionized water, the polyvinylpyrrolidone of 40mg is added, so
After weigh molybdenum disulphide powder powder stock 200mg and redox graphene powder raw material 20mg and be scattered in mixed solution,
It is configured to molybdenum disulfide suspension.Molybdenum disulfide suspension is transferred to progress liquid phase removing in ultrasonic pond, and to liquid phase ultrasound
Treated molybdenum disulfide suspension carries out centrifugal treating, and the supernatant at centrifuge tube 2/3rds is taken to obtain molybdenum disulfide/poly-
Vinylpyrrolidone/redox graphene dispersion liquid (i.e. molybdenum disulfide nano thin slice dispersion liquid), as catalytic hydrogen evolution activity
Material.
Using ink jet printing method by molybdenum disulfide/polyvinylpyrrolidone/redox graphene composite material spray printing in
Surface is covered on the polyimide base material of copper conductive film.It is as described below that it patterns configuration: first with planar graph (area
0.5*0.5cm2) spray printing 10 times, then with rectangular convolution line pattern spray printing 10 times, obtain having the catalysis of 3 D stereo configuration to analyse
Hydrogen working electrode.Linear sweep voltammetry characteristic present is carried out to the working electrode, characterization uses three-electrode system, electrolyte used
For 0.5M sulfuric acid solution, reference electrode used is silver/silver chloride electrode, and used is platinum plate electrode to electrode.
Fig. 9 is the linear sweep voltammetry curve for the polyimide-based three-dimensional catalytic hydrogen-precipitating electrode that comparative example 4 of the present invention obtains
Figure and Tafel curve graph.As shown in Figure 9, the polyimide-based three-dimensional catalytic hydrogen-precipitating electrode in comparative example 4 is in current density
10mA/cm2When overpotential of hydrogen evolution be 67mV, Tafel slope be 62mV/dec.
By embodiment 1 and comparative example 4 it is found that Teslin paper base is compared to Kapton substrate, due to its big table
Surface roughness increases active site quantity in unit area, to improve the catalytic hydrogen evolution performance of electrode.
The specific embodiment of the application above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
The limitation to the application protection scope therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, under the premise of not departing from technical scheme design, various modifications and improvements can be made, these belong to this
The protection scope of application.
Claims (9)
1. a kind of construction method of the catalytic hydrogen evolution electrode of abundant exposed molybdenum disulfide active sites, which is characterized in that including as follows
Step:
[1] preparation includes the dispersion liquid of molybdenum disulfide nano thin slice；
[2] using the dispersion liquid comprising molybdenum disulfide nano thin slice of step [1] preparation as printing ink, using ink jet printing method
Stereo graphic pattern molybdenum-disulfide radical catalytic hydrogen evolution electrode is formed in electrode basement.
2. a kind of construction method of the catalytic hydrogen evolution electrode of abundant exposed molybdenum disulfide active sites described in accordance with the claim 1,
It is characterized in that, it is described include the dispersion liquid of molybdenum disulfide nano thin slice the preparation method comprises the following steps:
[1-1] obtains the suspension comprising molybdenum disulfide nano thin slice using liquid phase ultrasound stripping method, shells in the liquid phase ultrasound
From adding surfactant in the removing solvent in method and accumulate inhibitor again；
The suspension comprising molybdenum disulfide nano thin slice that step [1-1] obtains is centrifuged in [1-2], takes 2/3rds
Place's supernatant obtains molybdenum-disulfide radical nano flake dispersion liquid.
3. a kind of construction method of the catalytic hydrogen evolution electrode of abundant exposed molybdenum disulfide active sites according to claim 2,
It is characterized by: the surfactant is polyvinylpyrrolidone.
4. a kind of construction method of the catalytic hydrogen evolution electrode of abundant exposed molybdenum disulfide active sites described in accordance with the claim 3,
It is characterized by: in step [1-1] the liquid phase ultrasound stripping process, be added the polyvinylpyrrolidone in removing solvent and
The mass ratio of molybdenum disulfide is 0.15~0.25:1.
5. a kind of construction method of the catalytic hydrogen evolution electrode of abundant exposed molybdenum disulfide active sites according to claim 2,
It is characterized by: the heavy accumulation inhibitor is redox graphene.
6. a kind of construction method of the catalytic hydrogen evolution electrode of abundant exposed molybdenum disulfide active sites according to claim 5,
It is characterized by: in step [1-1] the liquid phase ultrasound stripping process, be added redox graphene in removing solvent with
The mass ratio of molybdenum disulfide is 0.05~0.15:1.
7. a kind of construction method of the catalytic hydrogen evolution electrode of abundant exposed molybdenum disulfide active sites described in accordance with the claim 1,
It is characterized by: step [2] electrode basement is rigidity or flexibility that surface is covered with conductive film, that surface roughness is big
Substrate.
8. a kind of construction method of the catalytic hydrogen evolution electrode of abundant exposed molybdenum disulfide active sites described in accordance with the claim 1,
It is characterized in that, forming the process of stereo graphic pattern molybdenum-disulfide radical catalytic hydrogen evolution electrode in step [2] are as follows: first with planar graph
Spray printing is multiple, then multiple with rectangular convolution line or concentric circles spray printing.
9. a kind of construction method of the catalytic hydrogen evolution electrode of abundant exposed molybdenum disulfide active sites according to claim 8,
It is characterized in that, first with planar graph spray printing 10 times, then with rectangular convolution line or concentric circles spray printing 10-20 times.
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