CN109449439A - Cobalt molybdenum sulphur/graphene composite material preparation method and applications - Google Patents
Cobalt molybdenum sulphur/graphene composite material preparation method and applications Download PDFInfo
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- H—ELECTRICITY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The present invention relates to a kind of preparation method and applications of cobalt molybdenum sulphur/graphene composite material.The composite material is to follow the steps below preparation: a, preparing graphite oxide according to improved Hummers method；B, cobalt molybdenum sulphur (CoMoS) presoma is synthesized by chemical precipitation method；C, GO is placed in CoMoS precursor solution, hydrazine hydrate (N is used under the conditions of oil bath2H4·H2O it) restores, then in N2It is made annealing treatment under atmosphere；D, products therefrom salt acid soak, then cleaned with deionized water and ethyl alcohol, CoMoS/RGO composite material is made.Catalyst of the composite material as evolving hydrogen reaction (HER) shows excellent catalytic performance, and onset potential is only 28mV, and when current density reaches 10mA cm‑2When, potential is only 100mV.Under identical current density, with CoMoS made from same condition and bulk MoS2It compares, CoMoS/RGO composite material has apparent advantage.The present invention can also be extended to the design of other catalyst systems, provide new thinking for the further catalyst of development efficiently, inexpensive.
Description
Technical field:
The present invention relates to cobalt molybdenum sulphur/graphene composite material preparation method and its as catalyst in evolving hydrogen reaction
Using.
Background technique:
Energy crisis and environmental pollution force people to find a kind of reproducible clean energy resource to reduce disappearing for fossil fuel
Consumption.For hydrogen due to its energy density with higher and environmental-friendly advantage, being broadly considered most has application prospect
One of energy carrier.Electrochemical decomposition water is a kind of cost-effective hydrogen production process.Therefore, corresponding device needs efficient stable
Catalyst promote evolving hydrogen reaction (HER).Platinum (Pt) is most effective HER catalyst, but resource scarcity and cost at present
It is higher seriously to limit its application.In recent years, most of researchs about HER concentrate on finding a kind of money that can substitute Pt
Source material abundant is as catalyst.
Molybdenum disulfide due to its unique architectural characteristic and suction hydrogen free energy appropriate, be counted as it is a kind of it is efficient,
The HER catalyst of potential substitution Pt, receives people and widely pays close attention to.But the catalytic performance of molybdenum disulfide still cannot
Compare favourably, be primarily due to Pt: (1) the active position of molybdenum disulfide is few, and concentrates on edge, and surface is inert；(2) two
The electric conductivity of molybdenum sulfide itself is poor.For the catalytic performance for improving molybdenum disulfide, domestic and international scientific research personnel has been carried out largely
Research, achieves certain achievement.According to the literature, pass through regulation size and pattern, precious metal doping, manufacture sulphur vacancy
The methods of can increase the active position of molybdenum disulfide, improve its catalytic performance；By the way that molybdenum disulfide is preferable with electric conductivity
Material cladding, such as the carbon nano-fiber of graphene, three-dimensional porous metal, N doping can improve the electric conductivity of molybdenum disulfide,
Accelerate electrochemical reaction speed, improves its catalytic performance.Above method right and wrong for the catalytic performance for improving molybdenum disulfide
It is often effective, but the preparation process of higher cost and complexity restricts the development of catalyst.Molybdenum disulfide and cobalt are closed
Aurification can activate the surface of molybdenum disulfide, more active positions be made it have, while can also introduce impurity energy level, to increase
Add the electric conductivity of catalyst.In addition, graphene has biggish specific surface area and good electric conductivity, by cobalt molybdenum sulphur and graphene
Carry out it is compound, while improving catalyst electric conductivity, moreover it is possible to inhibit cobalt molybdenum sulfur nano particles to reunite, increase its active position,
To effectively improve the catalytic performance of catalyst.
Summary of the invention:
The object of the present invention is to provide cobalt molybdenum sulphur/graphene composite materials of a kind of combination chemical precipitation method and heat treatment
Preparation method and applications.In the composite material, the introducing of cobalt can activate the inert surface of molybdenum disulfide, make its active position
Increase, improves its catalytic performance, while can also introduce impurity energy level, improve the electric conductivity of catalyst；Graphene has biggish
Specific surface area and good electric conductivity, can effectively reduce the charge transfer resistance in electrochemical reaction process, and be able to suppress
Cobalt molybdenum sulfur nano particles are reunited, and are increased its active position, are conducive to improve catalytic performance.The composite material is as evolving hydrogen reaction
Catalyst shows excellent catalytic performance, has certain application prospect.The present invention can also be extended to other caltalysts
The design of system provides new thinking for the further catalyst of development efficiently, inexpensive.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of cobalt molybdenum sulphur/graphene composite material, comprising the following steps:
A, graphite oxide is synthesized according to improved Hummers method；
B, CoMoS presoma is synthesized by chemical precipitation method, by 0.262~0.272g (NH4)2MoS4With 0.232~
0.242g CoCl2·6H2O is dissolved in respectively in 20ml deionized water, is placed on magnetic stirring apparatus and is stirred, then by CoCl2It is molten
Liquid is added dropwise to (NH4)2MoS4In solution, there is black precipitate generation, which, which continues to be placed on magnetic stirring apparatus, stirs
30min；
C, 0.44~0.52ml graphite oxide is added to ultrasound 15min in the above-mentioned solution containing CoMoS presoma, so
It is placed in oil bath, under conditions of temperature is 95 DEG C, uses N2H4·H2O restores 0.5~1.5h, obtained black powder water
It is cleaned with ethyl alcohol, it is then dry in vacuum oven；
D, prepared black powder is placed in tube furnace, in N24~6h is kept the temperature in atmosphere under the conditions of 450~550 DEG C,
Products therefrom is impregnated with HCl, then is cleaned respectively with water and ethyl alcohol, and CoMoS/RGO composite material is obtained after drying.
It, need to be by CoCl when preparing CoMoS presoma when preparing CoMoS/RGO composite material in the step b2Solution by
It is added dropwise to (NH4)2MoS4In solution, prevent precipitating from assembling, size is uneven.
When preparing CoMoS/RGO composite material in the step c, graphite oxide is added to containing the molten of CoMoS presoma
After liquid, mixed solution need to be ultrasonically treated, two kinds of substances can be made uniformly to mix, come into full contact with.
The CoMoS presoma and RGO mixture are placed in N in the step d2It anneals in atmosphere, it is therefore an objective to will
CoMoS presoma, which decomposes, generates CoMoS, while enhancing the reciprocation in composite material between each ingredient.
The cobalt molybdenum sulphur/graphene composite material carries out electro-chemical test as catalyst, comprising the following steps:
A, first 2~4mg composite material (CoMoS/RGO) is dispersed in 0.4~0.6ml water/isopropanol/naphthol solution,
Then 20~40min of ultrasound obtains catalyst prepared Chinese ink solution.15~25 μ l catalyst solutions drop is taken out on glass-carbon electrode,
It dries at room temperature, forms uniform catalyst film；
B, electro-chemical test carries out in three electrode test systems of a standard, and the electrode wherein prepared in step a is made
For working electrode, carbon electrode is used as to electrode, and for calomel electrode as reference electrode, concentration is the H of 0.4~0.6M2SO4Solution
As electrolyte；
C, the CoMoS/RGO composite material is used to carry out on Ivium-n-Stat electrochemical workstation as working electrode
Test, polarization curve test carries out in the rotating disk electrode (r.d.e) that rotation speed is 2025rpm, relative to reversible hydrogen electrode
Potential scan range is 0~-0.4V, and scanning speed is 5mV s-1；Electrochemical impedance map is relative to reversible hydrogen electrode
Potential is under the constant voltage of -0.15V, and frequency is 100K Hz~0.1Hz；Current versus time curve test is relative to reversible
The potential of hydrogen electrode is sweep time 20000s under the constant voltage of -0.08V；
D, catalyst of the CoMoS/RGO composite material of preparation as evolving hydrogen reaction, shows excellent catalytic performance, rises
Beginning potential is only 28mV, and when current density is 10mA cm-2When, potential is only 100mV, under identical current density, with
With the MoS of CoMoS made from condition and bulk2It compares, there is apparent advantage.
The solution have the advantages that:
The present invention has synthesized a kind of efficient catalyst by simple method, by MoS2It is multiple with RGO again with Co alloying
It closes and CoMoS/RGO is made, which has good electric conductivity, the electricity that can be effectively reduced in electrochemical reaction process
The introducing of lotus transfer resistance, Co can activate MoS2Surface, increase its active position, while can also introduce impurity energy level, make
Electric conductivity is improved, thus shows excellent catalytic performance.
Detailed description of the invention:
The polarization curve of different catalysts in Fig. 1, the embodiment of the present invention 1.
The FESEM photo of the CoMoS/RGO composite material prepared in Fig. 2, the embodiment of the present invention 1.
The FESEM photo of the CoMoS prepared in Fig. 3, the embodiment of the present invention 1.
The TEM photo of the CoMoS/RGO composite material prepared in Fig. 4, the embodiment of the present invention 1.
The HRTEM photo of the CoMoS/RGO composite material prepared in Fig. 5, the embodiment of the present invention 1.
The XRD diffracting spectrum of the CoMoS/RGO composite material prepared in Fig. 6, the embodiment of the present invention 1.
The Raman map of the CoMoS/RGO composite material prepared in Fig. 7, the embodiment of the present invention 1.
The BET map of the CoMoS/RGO composite material prepared in Fig. 8, the embodiment of the present invention 1.
The XPS spectrum of the CoMoS/RGO composite material prepared in Fig. 9, the embodiment of the present invention 1.
The region the Mo 3d high-resolution XPS spectrum of the CoMoS/RGO composite material prepared in Figure 10, the embodiment of the present invention 1.
The region the S 2p high-resolution XPS spectrum of the CoMoS/RGO composite material prepared in Figure 11, the embodiment of the present invention 1.
The region the C 1s high-resolution XPS spectrum of the CoMoS/RGO composite material prepared in Figure 12, the embodiment of the present invention 1.
The region the Co 2p high-resolution XPS spectrum of the CoMoS/RGO composite material prepared in Figure 13, the embodiment of the present invention 1.
The Tafel curve of different catalysts in Figure 14, the embodiment of the present invention 1.
The electrochemical impedance map of different catalysts in Figure 15, the embodiment of the present invention 1.
When m- electric current of the CoMoS/RGO composite material prepared in Figure 16, the embodiment of the present invention 1 under constant voltage is close
Spend relation curve (illustration is FESEM photo of the CoMoS/RGO composite material after 20000s stability test).
The FESEM photo of the CoMoS/RGO composite material prepared in Figure 17, the embodiment of the present invention 2.
The FESEM photo of the CoMoS/RGO composite material prepared in Figure 18, the embodiment of the present invention 3.
Specific embodiment:
Particular content and embodiment of the invention are further illustrated now in conjunction with embodiment, however the embodiment is only
As explanation is provided, the restriction to technical solution of the present invention cannot be constituted.Embodiment 2,3 and 1 content phase of embodiment in the present invention
Closely, it is now described in detail by taking embodiment 1 as an example.
Embodiment 1
Preparation process in the present embodiment and steps are as follows:
(1) graphite oxide is synthesized according to improved Hummers method；
(2) CoMoS presoma is synthesized by chemical precipitation method, by 0.267g (NH4)2MoS4With 0.237g CoCl2·6H2O
It is dissolved in 20ml deionized water respectively, is placed on magnetic stirring apparatus and stirs, then by CoCl2Solution is added dropwise to (NH4)2MoS4In solution, there is black precipitate generation, which, which continues to be placed on magnetic stirring apparatus, stirs 30min；
(3) 0.48ml graphite oxide is added to ultrasound 15min in the above-mentioned solution containing CoMoS presoma, then set
In oil bath, under conditions of temperature is 95 DEG C, N is used2H4·H2O restores 1h, and obtained black powder is cleaned with water and ethyl alcohol,
Then dry in vacuum oven；
(4) prepared black powder is placed in tube furnace, in N25h is kept the temperature in atmosphere under the conditions of 500 DEG C, gained produces
Object salt acid soak, then cleaned respectively with water and ethyl alcohol, CoMoS/RGO composite material is obtained after drying；
(5) 3mg composite material (CoMoS/RGO) is dispersed in 0.5ml water/isopropanol/naphthol solution, it is then ultrasonic
30min obtains catalyst prepared Chinese ink solution.20 μ l catalyst solutions drop is taken out on glass-carbon electrode as working electrode, calomel electricity
As reference electrode, concentration is the H of 0.5M for pole2SO4For solution as electrolyte, the three-electrode system for forming standard carries out electrochemistry
Test；
(6) use the CoMoS/RGO composite material enterprising in Ivium-n-Stat electrochemical workstation as working electrode
Row test, polarization curve test carries out in the rotating disk electrode (r.d.e) that rotation speed is 2025rpm, relative to reversible hydrogen electrode
Potential scan range be 0~-0.4V, scanning speed be 5mV s-1；Electrochemical impedance map is relative to reversible hydrogen electrode
Potential be -0.15V constant voltage under, frequency be 100K Hz~0.1Hz；Current versus time curve test is relative to can
Under the constant voltage that the potential of inverse hydrogen electrode is -0.08V, sweep time 20000s；
The pattern and structural characterization of CoMoS/RGO composite material:
The surface topography of CoMoS/RGO composite material is characterized by scanning electron microscope (SEM).Fig. 2 is CoMoS/RGO's
SEM photograph.As can be seen that CoMoS nanoparticle is uniformly distributed, diameter is about 70nm.And it is CoMoS nanometers obtained under the conditions of
Then size is different for particle (Fig. 3), there is apparent agglomeration.This illustrates that the presence of RGO in composite material can inhibit
CoMoS nanoparticle is reunited.Fig. 4 is the TEM photo of CoMoS/RGO, and CoMoS is cross-linked with each other with RGO, and RGO has good lead
Electrically, it as the substrate of composite material, can reduce catalyst internal resistance, accelerate electrochemical reaction speed；RGO can inhibit simultaneously
CoMoS nanoparticle is reunited, and more active positions are made it have.Fig. 5 is the HRTEM photo of CoMoS/RGO, and interplanar distance is
(002) crystal face of the crystal face of 0.624nm for CoMoS.Fig. 6 is the XRD diffracting spectrum of CoMoS/RGO composite material, is located at
26.4 ° of diffraction maximum is the diffraction maximum of RGO, and other diffraction maximums are the diffraction maximum of CoMoS (PDF card is 16-0439).
The structure of CoMoS/RGO composite material can be further characterized by Raman spectrum, as shown in Figure 7.Positioned at 377cm-1With
402cm-1Two characteristic peaks respectively correspond MoS2E1 2gAnd A1gVibration mode, and A1gIntensity be much higher than E1 2g.Due to pole
The dependence for changing polarization, perpendicular to the A of plane1gVibration mode is to be excited by edge termination, therefore illustrate that CoMoS/RGO has
There is the structure of edge termination, to have good HER catalytic activity.In addition, the presence of RGO can also be true by Raman spectrum
Fixed, two characteristic peaks are located at 1359cm-1(D band) and 1581cm-1The intensity ratio of (G band), D band and G band is ID/IG=
1.29, illustrate there is a large amount of defect in graphene.Fig. 8 is the N of CoMoS/RGO composite material2Absorption/desorption isotherm and aperture
It is distributed map.According to Brunauer-Emmer-Teller (BET) model and Barrett-Joyner-Halenda (BJH) method
The specific surface area for measuring composite material is 69.9m2/g.In addition, it can be seen that, the aperture size in composite material is divided from illustration
Cloth is in 3~25nm, mainly due to MoS2The unordered of nanometer sheet and RGO two kinds of two-dimensional materials is self-assembly of.This some holes
It exists for catalyst and provides more active sites, promote H+Diffusion, to accelerate HER process.Fig. 9 is CoMoS/
The full spectrogram of the XPS of RGO composite material, it is known that contain elements Mo, S, Co, C and O in composite material.Figure 10, Figure 11, Figure 12 and figure
13 be respectively the high-resolution XPS spectrum of Mo 3d, S 2p, C 1s and Co 2p.Mo 3d is divided into 6 fitting peaks in Figure 10,
It wherein, is MoS positioned at the peak of 226.5eV2S 2s characteristic peak；Two characteristic peaks positioned at 229.2eV and 232.3eV are MoS2
Mo 3d5/2And 3d3/2, and the Mo 3d that combining can be relatively high5/2(229.5eV) and Mo 3d3/2(232.8eV) is because of Mo5+
Presence；Positioned at the Mo of 235.9eV6+The presence of characteristic peak be then caused by being oxidized as a small amount of sample.It is combined in Figure 11
It can be the S 2p of 162.0eV and 163.2eV3/2With S 2p1/2For MoS2In S2-, and in conjunction with can be for 162.7eV and 164.1eV
S 2p3/2With S 2p1/2It is due to S2 2-Presence, illustrate MoS2Marginal position increases, and is conducive to improve HER performance.C- in Figure 12
The peak intensity of O and C=O is very weak, illustrates that most of oxygen-containing functional group is successfully removed in RGO.Co 2p spectrum can be intended in Figure 13
Be combined into 4 pairs of characteristic peaks: first pair is the 2p for being located at the CoMoS phase of 779.2eV and 794.1eV3/2And 2p1/2；Second pair is to be located at
The Co of 780.5eV and 796.9eV2+2p3/2And 2p1/2；Third to and the 4th pair be satellites.
At room temperature, the catalytic performance characterization of CoMoS/RGO composite material:
Electrochemistry experiment is carried out using three electrode test systems of standard.As shown in Figure 1, Pt/C has best catalysis living
Property, onset potential 0mV, current density is 10mA cm-2When, potential only has 38mV.Bulk MoS2The poorly conductive of itself, work
Property position is few, thus shows poor HER catalytic activity.With the MoS of bulk2It compares, CoMoS has lower starting electricity
Gesture, this is because the introducing of Co makes MoS2Inert surface is activated, thus catalytic performance is improved.CoMoS/RGO is compound
Material shows more excellent catalytic performance, and onset potential is only 28mV, and when current density is 10mA cm-2When, it is excessively electric
Gesture is only 100mV.So excellent performance is mainly Co, RGO and MoS2The result of synergistic effect: (1) introducing of Co can activate
MoS2Inert surface increases its active position, improves its catalytic performance, while can also introduce impurity energy level, improve catalysis
The electric conductivity of agent；(2) RGO has biggish specific surface area and good electric conductivity, efficiently reduces electrochemical reaction process
In charge transfer resistance, and be able to suppress the reunion of CoMoS nanoparticle, increase its active position, be conducive to improve catalysis
The catalytic performance of agent.Figure 14 is corresponding Tafel curve.The Tafel slope of Pt/C is 31.0mV dec-1, with other documents
The result of report is consistent.Bulk MoS2, the Tafel slope of CoMoS and CoMoS/RGO are respectively 197.9mV dec-1,
145.6mV dec-1With 60.8mV dec-1.In addition to Pt/C, the Tafel slope of CoMoS/RGO composite material is minimum, illustrate with
The variation of potential, HER reaction rate variation it is most fast, this point can also prove composite material have excellent catalytic
Energy.Figure 15 is the electrochemical impedance map of CoMoS/RGO composite material, be can see by comparison, the MoS with bulk2With
CoMoS is compared, and the charge transfer resistance of CoMoS/RGO composite material is obviously reduced, be primarily due to the introducing of Co and RGO so that
The electric conductivity of composite material significantly improves.Figure 16 is when m- electricity of the CoMoS/RGO composite material at constant voltage (- 0.08V)
Current density relation curve.In the sweep time that have passed through 20000s, current density has decayed 15%, this is because anti-in electrochemistry
During answering, H in electrolyte+The H that either generates in reaction process of consumption2The surface for having stayed in electrode makes active material not
It can be fully used, hinder the generation of electrochemical reaction.Illustration is that CoMoS/RGO composite material passes through 20000s in Figure 16
FESEM photo after stability test, it can be seen that CoMoS/RGO composite material still maintains its original structure, illustrates me
The composite material for preparing there is preferable cyclical stability.To sum up, CoMoS/RGO composite material has excellent electrocatalysis
Can, reason is: the electric conductivity of catalyst can be improved in the introducing of RGO and Co, effectively reduces in electrochemical reaction process
Charge transfer resistance；Co can activate MoS2Surface, increase its active position, while can also introduce impurity energy level, make to lead
It is electrically improved, thus shows excellent catalytic performance.
Embodiment 2
(1) graphite oxide is synthesized according to improved Hummers method；
(2) CoMoS presoma is synthesized by chemical precipitation method, by 0.267g (NH4)2MoS4With 0.237g CoCl2·6H2O
It is dissolved in 20ml deionized water respectively, is placed on magnetic stirring apparatus and stirs, then by CoCl2Solution is added dropwise to (NH4)2MoS4In solution, there is black precipitate generation, which, which continues to be placed on magnetic stirring apparatus, stirs 30min；
(3) 0.24ml graphite oxide is added to ultrasound 15min in the above-mentioned solution containing CoMoS presoma, then set
In oil bath, under conditions of temperature is 95 DEG C, N is used2H4·H2O restores 1h, and obtained black powder is cleaned with water and ethyl alcohol,
Then dry in vacuum oven；
(4) prepared black powder is placed in tube furnace, in N25h is kept the temperature in atmosphere under the conditions of 500 DEG C, gained produces
Object salt acid soak, then cleaned respectively with water and ethyl alcohol, CoMoS/RGO composite material is obtained after drying；
(5) 3mg composite material (CoMoS/RGO) is dispersed in 0.5ml water/isopropanol/naphthol solution, it is then ultrasonic
30min obtains catalyst prepared Chinese ink solution.20 μ l catalyst solutions drop is taken out on glass-carbon electrode as working electrode, calomel electricity
As reference electrode, concentration is the H of 0.5M for pole2SO4For solution as electrolyte, the three-electrode system for forming standard carries out electrochemistry
Test；
The SEM photograph of CoMoS/RGO composite material made from the present embodiment is as shown in figure 17.The present embodiment system as seen from the figure
Material prepared by standby composite material and embodiment 1 has similar pattern, all has more active position, is conducive to urge
Change the raising of performance.
Embodiment 3
(1) graphite oxide is synthesized according to improved Hummers method；
(2) CoMoS presoma is synthesized by chemical precipitation method, by 0.267g (NH4)2MoS4With 0.237g CoCl2·6H2O
It is dissolved in 20ml deionized water respectively, is placed on magnetic stirring apparatus and stirs, then by CoCl2Solution is added dropwise to (NH4)2MoS4In solution, there is black precipitate generation, which, which continues to be placed on magnetic stirring apparatus, stirs 30min；
(3) 1.2ml graphite oxide is added to ultrasound 15min in the above-mentioned solution containing CoMoS presoma, be subsequently placed in
In oil bath, under conditions of temperature is 95 DEG C, N is used2H4·H2O restores 1h, and obtained black powder is cleaned with water and ethyl alcohol, so
It is dry in vacuum oven afterwards；
(4) prepared black powder is placed in tube furnace, in N25h is kept the temperature in atmosphere under the conditions of 500 DEG C, gained produces
Object is impregnated with HCl, then is cleaned respectively with water and ethyl alcohol, and CoMoS/RGO composite material is obtained after drying；
(5) 3mg composite material (CoMoS/RGO) is dispersed in 0.5ml water/isopropanol/naphthol solution, it is then ultrasonic
30min obtains catalyst prepared Chinese ink solution.20 μ l catalyst solutions drop is taken out on glass-carbon electrode as working electrode, calomel electricity
As reference electrode, concentration is the H of 0.5M for pole2SO4For solution as electrolyte, the three-electrode system for forming standard carries out electrochemistry
Test；
The SEM photograph of CoMoS/RGO composite material made from the present embodiment is as shown in figure 18.The present embodiment system as seen from the figure
Material prepared by standby composite material and embodiment 1 and embodiment 2 has similar pattern, all has more active sites
It sets, is conducive to the raising of catalytic performance.This also absolutely proves that the scope of application of this experiment is wider.
Claims (5)
1. a kind of preparation method of cobalt molybdenum sulphur/graphene composite material, comprising the following steps:
A, graphite oxide is synthesized according to improved Hummers method；
B, CoMoS presoma is synthesized by chemical precipitation method, by 0.262~0.272g (NH4)2MoS4With 0.232~
0.242gCoCl2·6H2O is dissolved in respectively in 20ml deionized water, is placed on magnetic stirring apparatus and is stirred, then by CoCl2Solution
It is added dropwise to (NH4)2MoS4In solution, there is black precipitate generation, which, which continues to be placed on magnetic stirring apparatus, stirs 30min；
C, 0.44~0.52ml graphite oxide is added to ultrasound 15min in the above-mentioned solution containing CoMoS presoma, then set
In oil bath, under conditions of temperature is 95 DEG C, N is used2H4·H2O restores 0.5~1.5h, obtained black powder water and second
Alcohol cleaning, it is then dry in vacuum oven；
D, prepared black powder is placed in tube furnace, in N24~6h, gained are kept the temperature in atmosphere under the conditions of 450~550 DEG C
Product salt acid soak, then cleaned respectively with water and ethyl alcohol, cobalt molybdenum sulphur/graphene CoMoS/RGO composite material is obtained after drying.
2. a kind of preparation method of cobalt molybdenum sulphur/graphene composite material according to claim 1, which is characterized in that step b
In, it, need to be by CoCl when preparing CoMoS presoma2Solution is added dropwise to (NH4)2MoS4In solution, prevent precipitating from assembling, size
Unevenly.
3. a kind of preparation method of cobalt molybdenum sulphur/graphene composite material according to claim 1, which is characterized in that step c
In, after graphite oxide is added to the solution containing CoMoS presoma, mixed solution need to be ultrasonically treated, two kinds of objects can be made
Matter is uniformly mixed, is come into full contact with.
4. a kind of preparation method of cobalt molybdenum sulphur/graphene composite material according to claim 1, which is characterized in that step d
In, the CoMoS presoma and RGO mixture are placed in N2It anneals in atmosphere, effect is to decompose CoMoS presoma to give birth to
At CoMoS, while enhancing the reciprocation in composite material between each ingredient.
5. cobalt molybdenum sulphur/graphene composite material preparation method composite material that the method according to claim 11 obtains,
Electro-chemical test is carried out as catalyst, comprising the following steps:
A, first 2~4mg CoMoS/RGO composite material is dispersed in 0.4~0.6ml water/isopropanol/naphthol solution, is then surpassed
20~40min of sound obtains catalyst prepared Chinese ink solution, takes out 15~25 μ l catalyst solutions drop on glass-carbon electrode, at room temperature
It is dry, form uniform catalyst film；
B, electro-chemical test carries out in three electrode test systems of a standard, and the electrode wherein prepared in step a is as work
Make electrode, carbon electrode is used as to electrode, and for calomel electrode as reference electrode, concentration is the H of 0.4~0.6M2SO4Solution conduct
Electrolyte；
C, the CoMoS/RGO composite material is used to be surveyed on Ivium-n-Stat electrochemical workstation as working electrode
Examination, polarization curve test carries out in the rotating disk electrode (r.d.e) that rotation speed is 2025rpm, in the electricity relative to reversible hydrogen electrode
Gesture scanning range is 0~-0.4V, and scanning speed is 5mV s-1；The test of electrochemical impedance map is relative to reversible hydrogen electrode
Potential be -0.15V constant voltage under, frequency be 100K Hz~0.1Hz；Current versus time curve test is relative to can
Under the constant voltage that the potential of inverse hydrogen electrode is -0.08V, sweep time 20000s；
D, catalyst of the CoMoS/RGO composite material of preparation as evolving hydrogen reaction, onset potential is only 28mV, and works as electric current
Density is 10mA cm-2When, potential is only 100mV, and under identical current density, catalytic performance is better than with made from condition
The MoS of CoMoS and bulk2。
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109935823A (en) * | 2019-04-08 | 2019-06-25 | 东北师范大学 | A kind of flexible lithium ion battery negative electrode material and its preparation method and application |
| CN110252348A (en) * | 2019-07-01 | 2019-09-20 | 青岛科技大学 | A kind of preparation method of the transition metal molybdenum sulphur gel elctro-catalyst of super hydrophilic super thin gas |
| CN110571414A (en) * | 2019-08-05 | 2019-12-13 | 上海工程技术大学 | Preparation method of sodium ion battery negative electrode material |
| CN110586156A (en) * | 2019-09-03 | 2019-12-20 | 天津大学 | Preparation method for synthesizing mesoporous nitrogen-doped graphene-loaded molybdenum disulfide through laser irradiation and application of mesoporous nitrogen-doped graphene-loaded molybdenum disulfide in electro-catalysis hydrogen production |
| CN112023961A (en) * | 2020-09-09 | 2020-12-04 | 广西师范大学 | Based on P-MoS2Preparation method of @ CoP composite material total hydrolysis catalyst |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101393651B1 (en) * | 2010-06-09 | 2014-05-13 | 주식회사 루트제이제이 | Cathode active material for lithium secondary battery, manufacturing method for the same and lithium secondary battery comprising the same |
| CN106611837A (en) * | 2015-10-27 | 2017-05-03 | 上海交通大学 | Cobalt-intercalated molybdenum sulfide secondary battery material and preparation method and application thereof |
-
2018
- 2018-11-12 CN CN201811336005.6A patent/CN109449439B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101393651B1 (en) * | 2010-06-09 | 2014-05-13 | 주식회사 루트제이제이 | Cathode active material for lithium secondary battery, manufacturing method for the same and lithium secondary battery comprising the same |
| CN106611837A (en) * | 2015-10-27 | 2017-05-03 | 上海交通大学 | Cobalt-intercalated molybdenum sulfide secondary battery material and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| XIAOPING DAI等: "Co-Doped MoS2 Nanosheets with the Dominant CoMoS Phase Coated on Carbon as an Excellent Electrocatalyst for Hydrogen Evolution", 《ACS APPLIED MATERIALS & INTERFACES》 * |
| YAN-RU LIU等: "In situ sulfurized CoMoS/CoMoO4 shell–core nanorods supported on N-doped reduced graphene oxide (NRGO) as efficient electrocatalyst for hydrogen evolution reaction", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| 付长璟: "《石墨烯的制备、结构及应用》", 30 June 2017 * |
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| CN109935823B (en) * | 2019-04-08 | 2020-10-13 | 东北师范大学 | Flexible lithium ion battery negative electrode material and preparation method and application thereof |
| CN110252348A (en) * | 2019-07-01 | 2019-09-20 | 青岛科技大学 | A kind of preparation method of the transition metal molybdenum sulphur gel elctro-catalyst of super hydrophilic super thin gas |
| CN110571414A (en) * | 2019-08-05 | 2019-12-13 | 上海工程技术大学 | Preparation method of sodium ion battery negative electrode material |
| CN110586156A (en) * | 2019-09-03 | 2019-12-20 | 天津大学 | Preparation method for synthesizing mesoporous nitrogen-doped graphene-loaded molybdenum disulfide through laser irradiation and application of mesoporous nitrogen-doped graphene-loaded molybdenum disulfide in electro-catalysis hydrogen production |
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