CN110052278A - Core-shell structure ZnS@C@MoS2The preparation method and applications of catalyst - Google Patents
Core-shell structure ZnS@C@MoS2The preparation method and applications of catalyst Download PDFInfo
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Abstract
The invention discloses core-shell structure ZnS@C@MoS2The preparation method and applications of catalyst, the present invention synthesizes the ZnS nanosphere of uniform particle diameter by hydro-thermal method, then using self-assembly method in one layer of PDA film of ZnS nanosphere surface-assembled, using high temperature cabonization, strong acid etching processing, the surface in situ finally by one step hydro thermal method in the ZnS@C of etching grow ultra-thin MoS2Nanometer sheet, the experimental results showed that carbon shell can greatly improve ZnS@C@MoS2Electric conductivity, be effectively prevented MoS2The aggregation of nanometer sheet, the MoS of two-dimensional ultrathin2The structure of nanometer sheet is conducive to expose active site to greatest extent, shortens the transmission path of charge, makes ZnS@C@MoS2Show excellent chemical property, and ZnS@C@MoS2When testing 12h in alkaline electrolyte, conservation rate is up to 84%, illustrates ZnS@C@MoS2It has excellent stability.
Description
Technical field
The present invention relates to a kind of preparation methods of catalyst, and in particular to core-shell structure ZnS@C@MoS2The preparation of catalyst
Method and its application.
Background technique
Due to the burning of fossil fuel, global energy crisis and environmental pollution are two main problems of facing mankind.Hydrogen
Gas is as a kind of with high heating value, the efficient, green of zero greenhouse gas emission, renewable energy, it has also become is generally accepted
Energy substitution product.Electrochemical decomposition water hydrogen manufacturing is a kind of new and effective energy conversion mode, can it is unstable, be not easy to store
Electric energy stored in the form of hydrogen, but during electrolysis water, higher hydrogen-evolution overpotential will cause unnecessary energy
Source loss, it is therefore desirable to which efficient, stable Electrocatalytic Activity for Hydrogen Evolution Reaction agent reduces its overpotential.For now, it platinum base and is based on
The composite material of platinum is considered as efficient liberation of hydrogen catalyst, but since content of the platinum in the earth's crust is extremely low and it is expensive
Its large-scale application in the industry of price limit, therefore exploitation can be used for being mass produced and have efficient, stable
Base metal liberation of hydrogen catalyst becomes as the key of current development electrolysis water liberation of hydrogen technology.
More and more attention has been paid to wherein MoS in the field electrocatalytic hydrogen evolution (HER) for transient metal sulfide2It is a kind of
The transient metal sulfide most represented.For MoS2Hydrogen Evolution Performance (HER) research to trace back to 1970, research work
Person has found block-like MoS2And do not have HER activity, until 2005, Hinnemann etc. was theoretical by Density functional number (DFT)
To MoS2The gibbs free energy change △ G of edge molybdenum atom absorption hydrogen ion processHIt is calculated, analyzes this stratiform material
The hydrogen bond free energy of material finds MoS2Basal plane be without catalytic activity, and vulcanize Mo edge and hydrogen atom knot
Preferable HER performance can be had close to Pt by closing；Jaramillo et al. makes Mo using vapour deposition process under the conditions of ultravacuum
In H2It is deposited in S atmosphere in Au (inertia HER catalytic activity) substrate, obtains the MoS of stratiform2Piece has the edge Mo-S abundant
Position further confirms MoS2Active site is the marginal portion of the Mo of vulcanization.MoS2Semiconductor material, due to its compared with
The electric conductivity and nanometer sheet of difference are easy to happen the phenomenon accumulated again, so that its chemical property be made to have a greatly reduced quality, limit
It has been made in the application in water decomposition field；In addition by the monistic restriction of material, people have been extremely difficult to, high activity has been urged
The demand of agent.Therefore, the electric conductivity and active sites points that material how is promoted by design of material, are urged to be effectively improved
The performance of agent is the hot spot of current research.
Summary of the invention
To solve the above problems, the present invention synthesizes the ZnS nanosphere of uniform particle diameter by hydro-thermal method, self assembly is then used
Method is in one layer of PDA film of ZnS nanosphere surface-assembled, using high temperature cabonization, strong acid etching processing, finally by a step hydro-thermal
Surface in situ of the method in the ZnS@C of etching grows ultra-thin MoS2Nanometer sheet, ZnS@C@MoS2Show excellent electrochemistry
Can, and ZnS@C@MoS2With excellent electrocatalytic hydrogen evolution performance.
Above-mentioned purpose of the invention is achieved through the following technical solutions: core-shell structure ZnS@C@MoS2Catalyst, it is described to urge
Agent includes nucleome and the shell for being wrapped in core surface, and the nucleome is ZnS nanosphere, and the shell is followed successively by from inside to outside
C layers and MoS2Nanoscale twins.
One layer C layers, which are wrapped up, outside ZnS nanosphere obtains ZnS C core-shell structure.ZnS@C core-shell structure is etched with dilute HCl solution
Afterwards, using hydro-thermal method synthesis core shell structure ZnS@C@MoS2Catalyst
Core-shell structure ZnS@C@MoS2The preparation method of catalyst, comprising the following steps:
The preparation of step 1, ZnS nanosphere: by Zn (Ac)2·5H2O is dissolved into deionized water, obtains solution A；Then again
PVP is distributed in solution A, and is placed on magnetic stirring apparatus and stirs 6h, obtains solution B；Then the TAA solution that will be prepared
It is added in solution B, stirs 30min, be fitted into autoclave, in 180 DEG C of reaction 12h；Finally to after reaction, cooling,
Centrifuge washing is dried to obtain ZnS nanosphere；
The preparation of step 2, ZnS@PDA: dispersing the ZnS nanosphere prepared in step 1 in dopamine-Tris-HCl,
It is protected from light and is stirred overnight, centrifuge washing, drying obtain ZnS@PDA；
The preparation of step 3, ZnS@C core-shell structure: the ZnS@PDA prepared in step 2 is calcined under protective gas, is obtained
ZnS@C core-shell structure；
Step 4, ZnS@C@MoS2Preparation:
(1) ZnS@C is pre-processed: the ZnS@C prepared in step 3 being dissolved into 0.1mol/L HCl solution, is stirred
30min, with deionized water centrifuge washing to neutrality, 60 DEG C of dryings；
(2) by ZnS@C and Na2MoO4·2H2O is dissolved into deionized water, after stirring 3h, obtains solution D, by TAA points
It is scattered in solution D, stirs 30min, be fitted into autoclave, for 24 hours in 200 DEG C of reactions；To after reaction, be subsequently cooled to
Room temperature, centrifuge washing, drying obtain ZnS@C@MoS2。
Preferably, in step 1, Zn (Ac)2·5H2O, deionized water, PVP, TAA amount ratio be 0.2g:20mL:2g:
0.075g；
In step 2, ZnS nanosphere, dopamine-Tris-HCl dosage be 200mg:200mL, wherein dopamine-Tris-
The pH of HCl is 8.5, and the concentration of dopamine is 2mg/mL.
In step 3, the heating rate used is calcined as 2 DEG C/min；Calcination temperature is 600 DEG C, calcination time 2h；It is described
Protection gas is N2；
In step 4, ZnS@C, Na2MoO4·2H2O, deionized water, TAA amount ratio be 10mg:100mg:15mL:
0.112g。
Core-shell structure ZnS@C@MoS2Catalyst is applied in electrolysis water liberation of hydrogen.It is made of the following steps:
Step A, by core-shell structure ZnS@C@MoS2 catalyst, ethyl alcohol, 5% naphthalene it is fragrant (mass fraction), ultrasonic disperse
30min obtains catalyst slurry；
Step B, it in the catalyst slurry drop-coated to nickel foam for obtaining step A, dries, suppresses flakiness, electrolysis is made
Elutriation hydrogen electrode；
Step C, take in step B be made electrolysis water hydrogen-precipitating electrode be working electrode, saturation calomel be reference electrode, platinum electrode
To be to carry out electrolysis water liberation of hydrogen in 1mol/mL KOH electrolyte in concentration to motor.
Preferably, in step A, the core-shell structure ZnS@C@MoS2Catalyst, ethyl alcohol, 5% naphthalene it is fragrant (mass fraction)
Amount ratio be 2mg:400uL:30uL；In step B, pressing pressure 8MP.
Compared with prior art, beneficial effects of the present invention:
(1) present invention synthesizes the ZnS nanosphere of uniform particle diameter by hydro-thermal method, then using self-assembly method at ZnS nanometers
Ball surface assembles one layer of PDA film, using high temperature cabonization, strong acid etching processing, finally by one step hydro thermal method in etching
The surface in situ of ZnS@C grows ultra-thin MoS2Nanometer sheet, the experimental results showed that carbon shell can greatly improve ZnS@C@MoS2
Electric conductivity, effectively prevent MoS2The aggregation of nanometer sheet, the MoS of two-dimensional ultrathin2The structure of nanometer sheet is conducive to expose to greatest extent
Active site shortens the transmission path of charge, makes ZnS@C@MoS2Show excellent chemical property；
(2)ZnS@C@MoS2When testing 12h in alkaline electrolyte, conservation rate is up to 84%, illustrates ZnS@C@MoS2Have
Excellent stability.
(3) in core-shell structure ZnS@C@MoS2 provided by the invention, there are hollow structures between carbon nanoshell and ZnS, can
Effectively to alleviate strain caused by volume change in cyclic process, ultra-thin MoS2 nanometer sheet electrode/electrolyte with higher
Interfacial surface area can effectively reduce the diffusion length of electronics and ion.
Detailed description of the invention
Fig. 1 (a-f) is core-shell structure ZnS@C@MoS of the present invention2The scanning electron microscope (SEM) photograph of catalyst, (a) ZnS, (b) ZnS@
PDA (c) ZnS@C, (d) ZnS@C@MoS2, (e) ZnS@MoS2, (f) MoS2Scanning electron microscope (SEM) photograph.
The transmission electron microscope picture of Fig. 2 (a) ZnS@C, (b-d) are ZnS@C@MoS2Transmission electron microscope picture, (e) be ZnS@C@MoS2
Mapping map.
The total spectrogram of Fig. 3 (a) catalyst product XRD；(b)ZnS@C；(c)MoS2XRD diagram.
Fig. 4 (a) is the linear sweep voltammetry curve of different catalysts, wherein (a1:ZnS@C@MoS2, a2:ZnS@C,
A3:ZnS, a4:MoS2, a5: blank Ni)；It (b) is the Tafel curve of different catalysts, wherein sweep speed is 2mV/s, electricity
Solve the KOH solution that liquid is 1mol/L.
Fig. 5 (a) ZnS@C@MoS2Polarization curve after enclosing cyclic voltammetry scan for start and process 500；(b) for certain
Chronoa mperometric plot under voltage.
Specific embodiment:
In order to better understand the present invention, below with reference to the embodiment content that the present invention is further explained, but the present invention
Content be not limited only to following embodiments.
Embodiment 1, core-shell structure ZnS@MoS2The preparation method of catalyst, comprising the following steps:
The preparation of step 1, ZnS
Firstly, weighing 0.2g Zn (Ac)2·5H2O is dissolved into 20mL deionized water；Then 2g PVP is distributed to again
It states in solution and is placed on magnetic stirring apparatus (mixing speed 400r/min) and stir 6h；Then, the TAA solution that will be prepared
(0.075g TAA is distributed in 20mL deionized water) is added drop-wise to dropwise in above-mentioned solution, and with magnetic stirring apparatus (mixing speed
400r/min) quickly it is fitted into 50mL autoclave, and 180 DEG C of holding 12h in air dry oven after stirring 30min；Most
Afterwards to after reaction, be cooled to room temperature, (deionized water, each 3 times of dehydrated alcohol) after product centrifuge washing is put in 60 DEG C of drums
It is dry in wind drying box.
The preparation of step 2, ZnS@C
First, prepare ZnS@PDA: dispersing the concentration that 200mL is prepared for the ZnS prepared in 200mg step 1 is 2mg/
In the dopamine-Tris-HCl of mL (pH=8.5), avoid light place is in stirred on magnetic stirring apparatus (mixing speed 400r/min)
Product is transferred to 60 DEG C of dryings in air dry oven by night, centrifuge washing (deionized water, each 3 times of dehydrated alcohol).
Prepare ZnS@C: by the above-mentioned ZnS@PDA prepared with the heating rate of 2 DEG C/min in N2The lower 600 DEG C of calcinings of atmosphere
2h is to get ZnS@C.
Step 3, preparation ZnS@C@MoS2
ZnS@C pretreatment: the ZnS@C prepared in step 2 is dissolved into 0.1mol/L HCl solution, magnetic agitation is placed on
30min is stirred on device, with deionized water centrifuge washing to neutrality, is placed in 60 DEG C of air dry ovens dry.
Step 4 weighs ZnS@C and the 100mg Na that 10mg is handled well2MoO4·2H2O is completely dissolved in 15mL deionized water
In, it is placed on after stirring 3h on magnetic stirring apparatus (mixing speed 400r/min), weighs 0.112g TAA and be distributed in above-mentioned solution
And 30min is quickly stirred, it is then charged into 20mL autoclave and is placed in air dry oven 200 DEG C and keep for 24 hours.To anti-
It after answering, is cooled to room temperature, (deionized water, each 3 times of dehydrated alcohol) after product centrifuge washing is put in 60 DEG C of forced air dryings
It is dry in case.
Wherein, ZnS@MoS2Preparation method: weigh 10mg for the ZnS prepared and be sufficiently dissolved into 15mL deionized water
In, then by 100mg Na2MoO4·2H2O is completely dissolved in above-mentioned solution, in magnetic stirring apparatus (mixing speed 400r/
Min it is fitted into 20mL autoclave after stirring 3h on), is kept for 24 hours for 200 DEG C in air dry oven.It is cold to after reaction
But to room temperature, (deionized water, each 3 times of dehydrated alcohol) after product centrifuge washing is put in 60 DEG C of baking ovens dry.
Application examples 1, ZnS@C@MoS2Catalyst electrolysis water liberation of hydrogen application test
ZnS, the ZnS@C and ZnS@C@MoS respectively prepared by embodiment 12Catalyst and MoS2Sample has carried out electrochemistry
Dependence test.
The ZnS, ZnS@C, ZnS@C@MoS of 2mg are taken respectively2、MoS2Catalyst takes 400uL ethyl alcohol, 30uL 5% respectively
Naphthalene sweet smell and different catalyst ultrasonic disperse 30min, obtain different catalyst slurries；Above-mentioned catalyst slurry is dripped respectively
It is applied in the nickel foam of 1*3cm, drop coating area 1*1cm dries, and 8MP pressure pushes flakiness, and electrolysis water hydrogen-precipitating electrode is made；
By obtained electrolysis water hydrogen-precipitating electrode be working electrode, saturation calomel is reference electrode, platinum electrode is to be in concentration to motor
Electrolysis water collecting gas is carried out in 1mol/mL KOH electrolyte.
Interpretation of result
Fig. 1 is the scanning electron microscope (SEM) photograph of gained different catalysts product in embodiment 1.ZnS prepared by Fig. 1 (a) embodiment 1
Scanning electron microscope (SEM) photograph, as can be seen from the figure ZnS be by little particle accumulate uniform ball shape structure, particle size 240nm
Left and right.Fig. 1 (b) is the scanning electron microscope (SEM) photograph of ZnS@PDA prepared by embodiment 1, it can be seen from the figure that covering one on the surface ZnS
Layer PDA film can not visually observe a nanometer little particle, and it is in uniform spherical distribution that ZnS@PDA, which remains unchanged, and partial size is compared
ZnS is increased slightly.Fig. 1 (c) is the scanning electron microscope (SEM) photograph of ZnS@C prepared by embodiment 1, and ZnS@PDA visually remains unchanged after calcining
It can be seen that ZnS nanometers of little particles, and the pattern of ZnS keeps good.Fig. 1 (d) be embodiment 1 in after hydrochloric acid is etched
ZnS@C Surface loads MoS in situ2Scanning electron microscopic picture, as can be seen from the figure MoS2Nanometer sheet assembles at random, and illustration is sample
The partial enlarged view of product, it can be seen that each nanometer sheet is buckle fold, and the edge of these folds is conducive to expose
More unsaturated sulphur atoms are so as to cause preferable electrochemistry Hydrogen Evolution Performance.Fig. 1 (e) is ZnS@prepared by embodiment 1
MoS2Scanning electron microscope (SEM) photograph, it can be seen from the figure that no C layers protect ZnS area load MoS2, we can be found that
ZnS nanosphere and MoS2Nanometer sheet separation, does not make MoS2Nanometer sheet is supported on ZnS nanosphere.Fig. 1 (f) is pure
MoS2The scanning electron microscope (SEM) photograph of nanometer sheet, it can be seen that MoS2It is distributed in the form of sheets and is laid in conductive base on the ground, be unfavorable for unsaturation
The sudden and violent leakage of sulphur atom, this result are consistent with electrocatalysis characteristic result.
Fig. 2 (a-c) is core-shell structure ZnS C MoS in embodiment 12Catalyst high-resolution TEM characterization result figure, catalysis
Agent ZnS@C@MoS2The catalytic performance with higher because of its unique structure.Fig. 2 (a) is by the ZnS@of acid etch certain time
The transmission electron microscope picture of C, the hollow core-shell nanostructure that display diameter is about 314nm, the thickness of carbon shell is about 35nm, coarse
Surface and porous structure are highly beneficial for the electron-transport in the electrocatalysis characteristic of HER.Fig. 2 (b) is sample ZnS@C@
MoS2The transmission electron microscope picture of low power, as can be seen from the figure chondritic surface successfully loads lamellar structure.Fig. 2 (c) is sample
The sectional view of product, as can be seen from the figure MoS2For lamellar structure.Fig. 2 (d) is the corresponding high power transmission electron microscope picture of sample, from
It can be seen that MoS in figure2Nanometer sheet edge spacing is greater than natural MoS2Piece spacing (0.62nm), this may be attributable to ZnS@C
Substrate effect, so as to cause formed extension interlamellar spacing structure.Fig. 2 (e) is ZnS@C@MoS2Mapping map, pass through
Distribution diagram of element can significantly observe the distribution situation of tetra- kinds of elements of Zn, Mo, C, S, as can be seen from Fig., these four members
Element covers selected whole region and illustrates this four element in ZnS C MoS2It is evenly distributed in sample.
Fig. 3 (b) is the X-ray powder diffraction pattern of ZnS prepared by embodiment 1, as can be seen from the figure the XRD card of ZnS
Piece and the position of ZnS@C diffraction maximum can coincide well, illustrate that there is no the crystal structures for changing ZnS after C doping, and
2 θ=28.6 °, 47.5 °, 56.3 ° of corresponding crystal faces are (111), (220), (311) and ZnS standard card (JCPDS card
Number 05-0566) it can be very good to match, illustrate that the sample is ZnS.Fig. 3 (c) is pure MoS2X-ray powder diffraction figure
Spectrum, the stronger diffraction maximum that product occurs near 2 θ=14.4 ° are the characteristic peaks for the molybdenum disulfide that corresponding crystal face is (002),
Illustrate that product has preferable layer structure, and at 33.7 °, 40 °, 58.3 ° respectively correspond (100), (103), (110) crystal face,
It can determine that the product synthesized at 200 DEG C is molybdenum disulfide substantially.Fig. 3 (a) is ZnS@C@MoS prepared by embodiment 32It is compound
The XRD diagram of material, it can be seen from the figure that still having apparent diffraction maximum at 28.6 ° at 47.5 °, 56.3 °, illustrating with molybdenum source
Addition there is no change ZnS crystal structure, in addition, relative to pure MoS2Diffraction maximum, composite material is at 14.4 °
(002) diffraction maximum of crystal face slightly shifts to the right and appears near 17.8 °, shows that molybdenum disulfide nano sheet interfloor distance increases
Greatly, this is just consistent with the result of TEM.There are the characteristic peak of apparent molybdenum disulfide, explanation at 33.7 °, 40 °, 58.3 °
MoS2Presence, in addition relative to pure molybdenum disulfide, the diffraction peak intensity of composite material is relatively weak, illustrates crystallinity not
It is good.
Fig. 4 (a) provides linear sweep voltammetry (LSV) curve of test sample in application examples 1, and all tests are in room temperature
It is obtained under static conditions.It can be seen from the figure that exposed NF electrode is almost without catalytic activity, and ZnS@C@MoS2It shows
Excellent HER performance, current density increase sharply with the increase of applied voltage, it is only necessary to the mistake of 69mV, 118mV and 180mV
Current potential can reach 1,10 and 50mA cm-2Current density.
In order to be compared, we also test pure MoS respectively2, ZnS and ZnS@C linear scan curve (table 1),
As can be seen from the table, the hydrogen evolution activity of ZnS is worst, due to its higher liberation of hydrogen crosses point, hydrogen evolution activity is poor；Work as ZnS
On area load after one layer of C film, relative to ZnS@C, when current density is 10mA cm-2When overpotential of hydrogen evolution reduce 15mV, this
It is mainly due to the addition of C, is conducive to increase the electric conductivity of sample to promote the catalytic activity of sample； MoS2It is close in electric current
Degree is 10mA cm-2When overpotential of hydrogen evolution only have 188mV, show poor catalytic activity, this is primarily due to MoS2Tiling
On the electrode, it is unfavorable for leaking more active site cruelly, this result is consistent with surface sweeping Electronic Speculum result.
All overpotentials of the invention are relative to standard hydrogen electrode (RHE), and all data carry out
Solution internal resistance (iR) compensation.
It is 10mA cm that the electrochemical parameter of 1 different materials of table, which is a) wherein current density,-2Liberation of hydrogen overpotential；It b) is electricity
Current density is 50mA cm-2Liberation of hydrogen overpotential；It c) is Tafel slope
For the evolving hydrogen reaction mechanism of further Study of Catalyst, we have studied the Tafel slopes of different catalysts.
Tafel slope is also an important parameter for measuring catalyst activity, and Ta Feier is smaller, illustrates to increase identical current density
When required current density it is smaller, catalyst activity is better.Fig. 4 (b) shows that the Ta Feier of different catalysts is oblique
Rate, we can see that ZnS@C@MoS from table 12Tafel slope only have 55.4mV/dec, be much smaller than ZnS
(155.4mV/dec), ZnS@C (97.7mV/dec) and MoS2(100.2mV/dec) according to classical theory, it falls in 40-
In the range of 120mV/dec, therefore ZnS@C@MoS2HER should pass through Volmer-Heyrovsky mechanism, electrochemistry
Desorption is rate determining step.
Its electrochemical stability test of another important evaluation criterion of liberation of hydrogen catalyst, Fig. 5 (a) show composite wood
Expect the linear surface sweeping volt-ampere curve of the circle of cyclic voltammetry scan 500 front and back, surface sweeping range is -0.4~0V (vs.RHE), scanning speed
Rate is 20mV/s as can be seen from the figure by prolonged circulation, and the current density of composite material only has variation slightly, because
This composite catalyst has preferable catalytic stability.Meanwhile it being carried out using stability of the chronoptentiometry to catalyst
Further verifying, as shown in Fig. 5 (b), by being up to 12h ZnS@C@MoS2The foam nickel electrode conservation rate modified is up to
87% or more, therefore excellent stability is shown, there is longer service life.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should all cover in protection scope of the present invention.
Claims (6)
1. core-shell structure ZnS@C@MoS2Catalyst, which is characterized in that the catalyst includes nucleome and is wrapped in core surface
Shell, the nucleome are ZnS nanosphere, and the shell is followed successively by C layers and MoS from inside to outside2Nanoscale twins.
2. core-shell structure ZnS@C@MoS described in claim 12The preparation method of catalyst, which is characterized in that including following step
It is rapid:
The preparation of step 1, ZnS nanosphere: by Zn (Ac)2·5H2O is dissolved into deionized water, obtains solution A；Then again will
PVP is distributed in solution A, is stirred 6h, is obtained solution B；Then the TAA solution prepared is added in solution B, after stirring 30min,
It is fitted into autoclave, in 180 DEG C of reaction 12h；Finally to after reaction, cooling, centrifuge washing are dried to obtain ZnS and receive
Rice ball；
The preparation of step 2, ZnS@PDA: it disperses the ZnS nanosphere prepared in step 1 in dopamine-Tris-HCl, is protected from light
It is stirred overnight, centrifuge washing, drying, obtains ZnS@PDA；
The preparation of step 3, ZnS@C core-shell structure: the ZnS@PDA prepared in step 2 is calcined under protective gas, obtains ZnS@
C core-shell structure；
Step 4, ZnS@C@MoS2Preparation:
(1) ZnS@C is pre-processed: the ZnS@C prepared in step 3 is dissolved into 0.1mol/L HCl solution, 30min is stirred, from
The heart is washed to neutrality, 60 DEG C of dryings；
(2) by ZnS@C and Na2MoO4·2H2O is dissolved into deionized water, is stirred 3h, is obtained solution D, TAA is distributed to solution
In D and 30min is stirred, is fitted into autoclave, for 24 hours in 200 DEG C of reactions；To after reaction, then cool to room temperature, from
Heart washing, drying, obtain ZnS@C@MoS2。
3. core-shell structure ZnS@C@MoS according to claim 22The preparation method of catalyst, which is characterized in that
In step 1, Zn (Ac)2·5H2O, deionized water, PVP, TAA amount ratio be 0.2g:20mL:2g:0.075g；
In step 2, ZnS nanosphere, dopamine-Tris-HCl dosage be 200mg:200mL, wherein dopamine-Tris-HCl
PH be 8.5, the concentration of dopamine is 2mg/mL.
In step 3, the heating rate used is calcined as 2 DEG C/min；Calcination temperature is 600 DEG C, calcination time 2h；The protection
Gas is N2；
In step 4, ZnS@C, Na2MoO4·2H2O, deionized water, TAA amount ratio be 10mg:100mg:15mL:0.112g.
4. core-shell structure ZnS@C@MoS described in claim 12The application of catalyst, which is characterized in that core-shell structure ZnS@C@
MoS2Catalyst is applied in electrolysis water liberation of hydrogen.
5. core-shell structure ZnS@C@MoS according to claim 42The application of catalyst, which is characterized in that by the following steps
Composition:
Step A, by core-shell structure ZnS@C@MoS2Catalyst, ethyl alcohol, 5% naphthalene it is fragrant, ultrasonic disperse 30min obtains catalyst slurry
Liquid；
Step B, it in the catalyst slurry drop-coated to nickel foam for obtaining step A, dries, suppresses flakiness, electrolysis elutriation is made
Hydrogen electrode；
Step C, take in step B be made electrolysis water hydrogen-precipitating electrode be working electrode, saturation calomel be reference electrode, platinum electrode is pair
Motor is that electrolysis water liberation of hydrogen is carried out in 1mol/mL KOH electrolyte in concentration.
6. core-shell structure ZnS@C@MoS according to claim 52The application of catalyst, which is characterized in that in step A, institute
State core-shell structure ZnS@C@MoS2Catalyst, ethyl alcohol, 5% naphthalene sweet smell amount ratio be 2mg:400uL:30uL；In step B, pressure
Pressing pressure is 8MP.
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