CN108441879B - Nanoporous nickel-molybdenum disulfide/graphene composite material preparation method and application - Google Patents
Nanoporous nickel-molybdenum disulfide/graphene composite material preparation method and application Download PDFInfo
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- CN108441879B CN108441879B CN201810232758.6A CN201810232758A CN108441879B CN 108441879 B CN108441879 B CN 108441879B CN 201810232758 A CN201810232758 A CN 201810232758A CN 108441879 B CN108441879 B CN 108441879B
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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Abstract
The present invention relates to a kind of nanoporous nickel-molybdenum disulfide/graphene composite material preparation method and applications.Molybdenum disulfide/graphene (the MoS that will be prepared respectively by hydro-thermal method2/ RGO) and nickel hydroxide [Ni (OH)2] mixing, nanoporous nickel-molybdenum disulfide/graphene (NPNi-MoS can be prepared by then carrying out annealing2/ RGO) composite material.The specific method is as follows: a, preparing graphite oxide according to improved Hummers method；B, MoS is prepared by hydro-thermal method2/RGO；C, Ni (OH) is prepared by hydro-thermal method2Powder；D, by Ni (OH)2With MoS2/ RGO is uniformly mixed and is placed in tube furnace, in Ar/H2It anneals under atmosphere, Ni (OH)2It is reduced into NPNi, NPNi-MoS is made2/ RGO composite material.Catalyst of the composite material as evolving hydrogen reaction (HER) shows excellent catalytic performance, onset potential 85mV, under identical current density, with MoS made from same condition2、MoS2/ RGO and NPNi-MoS2It compares, there is apparent advantage.The present invention can also be extended to the design of other catalyst, provide new thinking to develop efficient, low cost catalyst.
Description
Technical field:
The present invention relates to nanoporous nickel-molybdenum disulfide/graphene composite material preparation method and its as catalyst
Application in evolving hydrogen reaction.
Background technique:
Hydrogen energy density with higher and environmental-friendly advantage, are broadly considered the energy for most having application prospect
One of loading gage body.Platinum (Pt) is most effective evolving hydrogen reaction (HER) catalyst, but resource scarcity and higher cost seriously limit
Its application is made.In recent years, most of researchs about HER, which concentrate on finding one kind, can substitute Pt, resourceful
Material is as catalyst.In the catalyst of numerous alternative Pt, molybdenum disulfide is due to its unique architectural characteristic and appropriate
Hydrogen free energy is inhaled, is aroused widespread concern.
Theoretical modeling and experiment has been obtained as a kind of HER catalyst that is efficient, being expected to substitution Pt in molybdenum disulfide
As a result confirmation.But the development of molybdenum disulfide has nevertheless suffered from stern challenge, is primarily due to: (1) work of molybdenum disulfide
Property position is few, is concentrated mainly on edge, surface cannot be fully utilized；(2) electric conductivity of molybdenum disulfide itself is poor.
In order to improve the catalytic performance of molybdenum disulfide, domestic and international scientific research personnel has carried out a large amount of research, achieves some achievements.According to
Document report can increase the activity of molybdenum disulfide by size and the methods of Morphological control, metal-doped, manufacture sulphur vacancy
Its catalytic performance is improved in position；By by molybdenum disulfide and the preferable Material cladding of electric conductivity, such as graphene, three-dimensional porous gold
Category, carbon nano-fiber of N doping etc. can improve the electric conductivity of molybdenum disulfide, accelerate electrochemical reaction speed, improve its catalysis
Performance.The above method is very effective for the catalytic performance for improving molybdenum disulfide, but increase rate is not enough.Tool
The nanoporous nickel and graphene for having unique three-dimensional porous structure have biggish specific surface area and good electric conductivity, by two
Person and molybdenum disulfide progress are compound, while improving molybdenum disulfide electric conductivity, moreover it is possible to inhibit molybdenum disulfide stacking, increase its work
Property position, to effectively improve the catalytic performance of molybdenum disulfide.
Summary of the invention:
The object of the present invention is to provide a kind of combination hydro-thermal methods and the nanoporous of heat treatment nickel-molybdenum disulfide/graphene
The preparation method and application of composite material.In the composite material, graphene has good electric conductivity, and is able to suppress two
Molybdenum sulfide is reunited, it is made to be evenly distributed in the surface of graphene, and the charge efficiently reduced in electrochemical reaction process turns
Move resistance；Nanoporous nickel can be improved the catalytic activity of catalyst, and unique three-dimensional porous structure is also H+Transmission mention
More channels have been supplied, evolving hydrogen reaction rate is further improved.Catalyst of the composite material as evolving hydrogen reaction, shows
Excellent catalytic performance has certain application prospect.The present invention can also be extended to the design of other catalyst, high for development
Effect, inexpensive catalyst provide new thinking.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of nanoporous nickel-molybdenum disulfide/graphene composite material preparation method, comprising the following steps:
A, graphite oxide is synthesized according to improved Hummers method；
B, MoS is synthesized by hydro-thermal method2/ RGO composite material, first by 2.20~2.60g Na2S·9H2O and 0.68~
0.74gMoO3It is dissolved in 20ml deionized water, is placed on magnetic stirring apparatus and stirs, then by 2.2~2.6ml graphite oxide point
It dissipates in the above solution, is transferred in stainless steel cauldron after 10~20min of ultrasound, the reaction kettle of sealing is put into 180~220
40~80min is kept the temperature in DEG C electronics baking oven.Obtained MoS2/ RGO composite material cleans 2~6 times, ethyl alcohol with deionized water respectively
Cleaning 1~3 time, obtained black precipitate is put into 10~14h of heat preservation in 40~80 DEG C of vacuum ovens, then by collection of products；
C, Ni (OH) is prepared by hydro-thermal method2Powder, by 1.4~1.5g Ni (NO3)2·6H2O and 1.3~1.5g six times
Methenamine HMT is dissolved in 30~40ml ultrapure water, with magnetic stirrer it is uniform after be transferred to stainless steel cauldron
In, it is clear that the reaction kettle of sealing is put into 8~12h of heat preservation, obtained green powder water and ethyl alcohol in 80~120 DEG C of electronics baking ovens
It washes, it is then dry in vacuum oven；
D, by prepared Ni (OH)2With MoS2/ RGO is fully ground in the agate mortar to being uniformly mixed, then will mixing
Object is placed in tube furnace, in Ar/H24~6h is kept the temperature in mixed atmosphere under the conditions of 450~550 DEG C, prepares NPNi-MoS2/ RGO is multiple
Condensation material.
MoS is prepared in the step b2When/RGO composite material, sample is ultrasonically treated, two kinds of substance contacts can be made
More sufficiently, and it is effectively prevented MoS2Reunite.
The mixture is placed in Ar/H in the step d2It anneals in mixed gas, it is therefore an objective to by Ni (OH)2It is reduced into
NPNi, and further enhance the reciprocation in composite material between each ingredient.
Nanoporous nickel-molybdenum sulfide/the graphene composite material carries out electro-chemical test, packet as catalyst
Include following steps:
A, first by 1.5~2.5mg catalyst (NPNi-MoS2/ RGO) to be dispersed in 0.4~0.6ml water/isopropanol/naphthols molten
In liquid, then 20~40min of ultrasound, obtains catalyst prepared Chinese ink solution.20~40 μ l catalyst solutions drop is taken out in glass-carbon electrode
On, it is dried at room temperature for, 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, with the NPNi-MoS2/ RGO composite material carries out on CHI660E 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~-0.8V, and scanning speed is 5mV s-1；When carrying out cyclic voltammetry, relative to reversible hydrogen electrode
Potential scan range be -0.15~0.1V, scanning speed be 100mV s-1；Current versus time curve test is relative to can
Under the constant voltage that the potential of inverse hydrogen electrode is -0.19V, sweep time 30000s；
D, the NPNi-MoS of preparation2Catalyst of/RGO the composite material as evolving hydrogen reaction, shows excellent catalytic
Can, onset potential 85mV, under identical current density, with MoS made from same condition2、MoS2/ RGO and NPNi-MoS2Phase
Than having apparent advantage.
The solution have the advantages that:
NPNi-MoS produced by the present invention2/ RGO composite material has good electric conductivity, can be effectively reduced electrification
The charge transfer resistance in reaction process is learned, unique three-dimensional porous structure is while increasing catalyst active sites, also
For H+Diffusion provide more channels, thus show 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 NPNi-MoS prepared in Fig. 2, the embodiment of the present invention 12The FESEM photo of/RGO composite material.
The MoS prepared in Fig. 3, the embodiment of the present invention 12FESEM photo.
The MoS prepared in Fig. 4, the embodiment of the present invention 12The FESEM photo of/RGO composite material.
The NPNi-MoS prepared in Fig. 5, the embodiment of the present invention 12The FESEM photo of composite material.
The NPNi-MoS prepared in Fig. 6, the embodiment of the present invention 12The TEM photo of/RGO composite material.
The NPNi-MoS prepared in Fig. 7, the embodiment of the present invention 12The HRTEM photo of/RGO composite material.
The MoS prepared in Fig. 8, the embodiment of the present invention 12,MoS2/RGO,NPNi-MoS2And NPNi-MoS2/ RGO composite wood
The XRD diffracting spectrum of material.
The NPNi-MoS prepared in Fig. 9, the embodiment of the present invention 12The Raman map of/RGO composite material.
The NPNi-MoS prepared in Figure 10, the embodiment of the present invention 12The BET map of/RGO composite material.
The NPNi-MoS prepared in Figure 11, the embodiment of the present invention 12The XPS spectrum of/RGO composite material.
The NPNi-MoS prepared in Figure 12, the embodiment of the present invention 12The region the C 1s high-resolution XPS light of/RGO composite material
Spectrum.
The NPNi-MoS prepared in Figure 13, the embodiment of the present invention 12The region the Mo 3d high-resolution XPS light of/RGO composite material
Spectrum.
The NPNi-MoS prepared in Figure 14, the embodiment of the present invention 12The region the S 2p high-resolution XPS light of/RGO composite material
Spectrum.
The Tafel curve of different catalysts in Figure 15, the embodiment of the present invention 1.
The NPNi-MoS prepared in Figure 16, the embodiment of the present invention 12/ RGO composite material is initial and by 20000 circle circulations
Polarization curve comparison diagram afterwards.
The NPNi-MoS prepared in Figure 17, the embodiment of the present invention 12The when m- electricity of/RGO composite material under constant voltage
Current density relation curve.
The NPNi-MoS prepared in Figure 18, the embodiment of the present invention 22The FESEM photo of/RGO composite material.
The NPNi-MoS prepared in Figure 19, the embodiment of the present invention 32The FESEM photo of/RGO composite material.
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 and 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) MoS is synthesized by hydro-thermal method2/ RGO composite material, by 2.4g Na2S·9H2O and 0.72g MoO3It is dissolved in
In 20ml deionized water, 2.4ml graphite oxide is then added, is transferred in stainless steel cauldron after ultrasonic 15min, by sealing
Reaction kettle is put into 200 DEG C of electronics baking ovens and keeps the temperature 60min.Obtained MoS2/ RGO composite material cleans 4 with deionized water respectively
Secondary, ethyl alcohol cleans 2 times, and obtained black precipitate is put into 60 DEG C of vacuum ovens and keeps the temperature 12h, then by collection of products；
(3) Ni (OH) is prepared by hydro-thermal method2Powder, by 1.45g Ni (NO3)2It is molten with 1.4g hexamethylene tetramine HMT
Solution in 35ml ultrapure water, with magnetic stirrer it is uniform after be transferred in stainless steel cauldron, the reaction kettle of sealing is put
Enter in 100 DEG C of electronics baking ovens and keep the temperature 10h, by green product Ni (OH)2By being collected by centrifugation；
(4) by prepared Ni (OH)2With MoS2/ RGO grind in the agate mortar uniformly carry out it is compound, then will mixing
Object is placed in tube furnace, in Ar/H25h is kept the temperature in mixed atmosphere under the conditions of 500 DEG C, prepares NPNi-MoS2/ RGO composite material；
(5) by 2mg catalyst (NPNi-MoS2/ RGO) it is dispersed in 0.5ml water/isopropanol/naphthol solution, it is then ultrasonic
30min obtains catalyst prepared Chinese ink solution.30 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) with the NPNi-MoS2/ RGO composite material carries out on CHI660E 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~-0.8V, and scanning speed is 5mV s-1；When carrying out cyclic voltammetry, relative to reversible hydrogen electrode
Potential scan range be -0.15~0.1V, scanning speed be 100mV s-1；Current versus time curve test is relative to can
Under the constant voltage that the potential of inverse hydrogen electrode is -0.19V, sweep time 30000s；
NPNi-MoS2The pattern and structural characterization of/RGO composite material:
NPNi-MoS is characterized by field emission scanning electron microscope (FESEM)2The surface topography of/RGO composite material.Fig. 2 is
NPNi-MoS2The SEM photograph of/RGO.As can be seen that due to MoS2The size of nanometer sheet is smaller and the introducing of NPNi, NPNi-
MoS2/ RGO composite material and original MoS2(Fig. 3), MoS2/ RGO (Fig. 4) and NPNi-MoS2(Fig. 5), which is compared, to be had more
Active position, thus have preferable catalytic performance.Fig. 6 is NPNi-MoS2The TEM photo of/RGO, RGO have good lead
Electrically, it as the substrate of composite material, can reduce catalyst internal resistance, accelerate electrochemical reaction speed.Illustration is the TEM of NPNi
Photo, aperture 20nm, ligament width 40nm, this unique three-dimensional dual link nanostructure is in the electricity for increasing catalyst
While chemical activity area, the internal resistance of catalyst can also be reduced, and then improve the catalytic activity of catalyst.Fig. 7 is NPNi-
MoS2The HRTEM photo of/RGO, interplanar distance 0.623nm and 0.204nm correspond respectively to MoS2(002) crystal face and Ni
(111) crystal face.Fig. 8 is MoS2,MoS2/RGO,NPNi-MoS2And NPNi-MoS2The XRD diffracting spectrum of/RGO composite material, position
In 13.9 °, 33.3 °, 39.8 °, 58.6 ° and 69.2 ° of diffraction maximums be respectively 2H-MoS2(002), (100), (103),
(110) and (201) crystal face, and other diffraction maximums for being located at 44.4 °, 51.9 ° and 76.2 ° then respectively correspond (111) of Ni,
(200) and (220) crystal face.It was found that NPNi-MoS2The diffraction peak intensity of (002) crystal face of/RGO composite material is weaker than other three kinds
Catalyst material, this illustrates that the presence of RGO can inhibit MoS2Stacking, make it have more active positions.The presence of RGO
It can be determined by Raman spectrum, as shown in Figure 9.Two characteristic peaks of RGO are located at 1350cm-1(D band) and 1590cm-1
The intensity ratio of (G band), D band and G band is ID/IG=1.08, illustrate there is a large amount of defect in composite material.Figure 10 is NPNi-
MoS2The N of/RGO composite material2Absorption/desorption isotherm and pore-size distribution map.According to Brunauer-Emmer-Teller
(BET) it is 39.2m that model and Barrett-Joyner-Halenda (BJH) method, which measure the specific surface area of composite material,2/g.This
Outside, from being can see in composite material in illustration, there are two kinds of holes: the aperture size of aperture is distributed in 2~4nm, main
If due to single layer MoS2The unordered mesoporous channel being self-assembly of of nanometer sheet；Macropore is distributed in a wider size model
It encloses: 5~100nm, mainly due to Ni (OH)2It is reduced in annealing process and to be formed.These are mesoporous to exist for catalyst
More active sites are provided, H is promoted+Diffusion, to accelerate HER process.Figure 11 is NPNi-MoS2/ RGO composite wood
The full spectrogram of the XPS of material, it is known that contain elements Mo, C, O, S and Ni in composite material.Figure 12, Figure 13 and Figure 14 are respectively C 1s, Mo
The high-resolution XPS spectrum of 3d and S 2p.It can be recognized from fig. 12 that the characteristic peak positioned at 284.5eV is sp in graphite2The C of hydridization,
And alternatively bright most of oxygen-containing functional group is successfully removed the peak intensity of faint C-O.Figure 13 shows that Mo 3d can be divided
For 4 fitting peaks, wherein positioned at the peak of 226.2eV be MoS2S 2s characteristic peak；Positioned at two of 229.1eV and 232.3eV
Characteristic peak is Mo 3d5/2And 3d3/2, illustrate Mo in composite material4+It occupies an leading position；Positioned at the Mo of 235.4eV6+Characteristic peak
In the presence of being then caused by being oxidized as a small amount of sample.Combination can be the S 2p of 161.9eV and 163.1eV in Figure 143/2And S
2p1/2For MoS2In S2-。
At room temperature, NPNi-MoS2The catalytic performance of/RGO composite material characterizes:
Electrochemistry experiment is carried out using three electrode test systems of standard.As shown in Figure 1, due to MoS2The electric conductivity of itself
Difference, active position are few, thus show poor HER catalytic activity, onset potential 150mV.With original MoS2It compares,
MoS2/ RGO and NPNi/MoS2Onset potential be respectively 120mV and 100mV, there is preferable catalytic activity.RGO and NPNi are bis-
The NPNi-MoS of modification2/ RGO composite material exhibits go out more excellent catalytic performance, onset potential 85mV.It is so excellent
Performance be mainly NPNi, RGO and MoS2The result of synergistic effect: (1) NPNi can be improved the catalytic activity of catalyst, and
Its unique three-dimensional dual link porous structure is also H+Transmission provide more channels；(2)MoS2Nanometer sheet is distributed in RGO
Surface, charge transfer resistance is efficiently reduced, to accelerate electrochemical reaction speed.Figure 15 is corresponding Ta Feier bent
Line.MoS2,MoS2/ RGO and NPNi-MoS2Tafel slope be respectively 150.6mV dec-1,95.1mV dec-1With
147.6mV dec-1.Compared with above-mentioned three kinds of materials, NPNi-MoS2The Tafel slope of/RGO composite material is minimum, only
71.3mV dec-1.Tafel slope is lower, illustrates the variation with potential, and the reaction rate of HER changes faster, this point
It can prove that composite material has excellent catalytic properties.
Figure 16 is NPNi-MoS2The stability test of/RGO composite material by comparison as a result, can see, the catalyst
Polarization curve there is no variation after 20000 circle circulations, with good cyclical stability.In order to further demonstrate,prove
Its bright electrochemical stability, tests under the voltage of -0.19V, the relation curve of electric current and time, as shown in figure 18.As it can be seen that
In the sweep time that have passed through 30000s, current density has decayed 10%, this lesser current loss may be due in electricity
In chemical reaction process, H in electrolyte+The H that either generates in reaction process of consumption2The surface of electrode is stayed in, so that living
Property substance cannot be fully utilized, and hinder the generation of electrochemical reaction.To sum up, NPNi-MoS2/ RGO composite material has
Excellent catalytic performance and preferable cyclical stability, reason is: leading for catalyst can be improved in the introducing of RGO and NPNi
Electrically, the charge transfer resistance in electrochemical reaction process is effectively reduced；The unique three-dimensional porous structure of NPNi is urged in increase
It is also H while agent activity position+Diffusion provide more channels.
Embodiment 2
(1) graphite oxide is synthesized according to improved Hummers method；
(2) MoS is synthesized by hydro-thermal method2/ RGO composite material, by 2.4g Na2S·9H2O and 0.72g MoO3It is dissolved in
In 20ml deionized water, 1.2ml graphite oxide is then added, is transferred in stainless steel cauldron after ultrasonic 15min, by sealing
Reaction kettle is put into 200 DEG C of electronics baking ovens and keeps the temperature 60min.Obtained MoS2/ RGO composite material cleans 4 with deionized water respectively
Secondary, ethyl alcohol cleans 2 times, and obtained black precipitate is put into 60 DEG C of vacuum ovens and keeps the temperature 12h, then by collection of products；
(3) Ni (OH) is prepared by hydro-thermal method2Powder, by 1.45g Ni (NO3)2It is molten with 1.4g hexamethylene tetramine HMT
Solution in 35ml ultrapure water, with magnetic stirrer it is uniform after be transferred in stainless steel cauldron, the reaction kettle of sealing is put
Enter in 100 DEG C of electronics baking ovens and keep the temperature 10h, by green product Ni (OH)2By being collected by centrifugation；
(4) by prepared Ni (OH)2With MoS2/ RGO grind in the agate mortar uniformly carry out it is compound, then will mixing
Object is placed in tube furnace, in Ar/H25h is kept the temperature in mixed atmosphere under the conditions of 500 DEG C, prepares NPNi-MoS2/ RGO composite material；
(5) by 2mg catalyst (NPNi-MoS2/ RGO) it is dispersed in 0.5ml water/isopropanol/naphthol solution, it is then ultrasonic
30min obtains catalyst prepared Chinese ink solution.30 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；
NPNi-MoS made from the present embodiment2The SEM photograph of/RGO composite material is as shown in figure 18.This implementation as seen from the figure
The composite material of example preparation has similar pattern with material prepared by embodiment 1, all has more active position, favorably
In its catalytic performance.
Embodiment 3
(1) graphite oxide is synthesized according to improved Hummers method；
(2) MoS is synthesized by hydro-thermal method2/ RGO composite material, by 2.4g Na2S·9H2O and 0.72g MoO3It is dissolved in
In 20ml deionized water, 6ml graphite oxide is then added, is transferred in stainless steel cauldron after ultrasonic 15min, by the anti-of sealing
It answers kettle to be put into 200 DEG C of electronics baking ovens and keeps the temperature 60min.Obtained MoS2/ RGO composite material respectively with deionized water clean 4 times,
Ethyl alcohol cleans 2 times, and obtained black precipitate is put into 60 DEG C of vacuum ovens and keeps the temperature 12h, then by collection of products；
(3) Ni (OH) is prepared by hydro-thermal method2Powder, by 1.45g Ni (NO3)2It is molten with 1.4g hexamethylene tetramine HMT
Solution in 35ml ultrapure water, with magnetic stirrer it is uniform after be transferred in stainless steel cauldron, the reaction kettle of sealing is put
Enter in 100 DEG C of electronics baking ovens and keep the temperature 10h, by green product Ni (OH)2By being collected by centrifugation；
(4) by prepared MoS2/ RGO and Ni (OH)2Grind in the agate mortar uniformly carry out it is compound, then will mixing
Object is placed in tube furnace, in Ar/H25h is kept the temperature in mixed atmosphere under the conditions of 500 DEG C, prepares NPNi-MoS2/ RGO composite material；
(5) by 2mg catalyst (NPNi-MoS2/ RGO) it is dispersed in 0.5ml water/isopropanol/naphthol solution, it is then ultrasonic
30min obtains catalyst prepared Chinese ink solution.30 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；
NPNi-MoS made from the present embodiment2The SEM photograph of/RGO composite material is as shown in figure 19.This implementation as seen from the figure
The composite material of example preparation has similar pattern with material prepared by embodiment 1 and embodiment 2, all has more activity
Position is conducive to its catalytic performance.
Claims (4)
1. a kind of nanoporous nickel-molybdenum disulfide/graphene composite material preparation method, comprising the following steps:
A, graphite oxide is synthesized according to improved Hummers method；
B, MoS is synthesized by hydro-thermal method2/ RGO composite material, first by 2.20~2.60g Na2S·9H2O and 0.68~0.74g
MoO3It is dissolved in 20ml deionized water, is placed on magnetic stirring apparatus and stirs, be then dispersed in 2.2~2.6ml graphite oxide
It in above-mentioned solution, is transferred in stainless steel cauldron after 10~20min of ultrasound, the reaction kettle of sealing is put into 180~220 DEG C of electricity
40~80min, obtained MoS are kept the temperature in sub- baking oven2/ RGO composite material cleans 2~6 times, ethyl alcohol cleaning with deionized water respectively
1~3 time, obtained black precipitate is put into 10~14h of heat preservation in 40~80 DEG C of vacuum ovens, then by collection of products；
C, Ni (OH) is prepared by hydro-thermal method2Powder, by 1.4~1.5g Ni (NO3)2·6H2Six methylene of O and 1.3~1.5g
Tetramine HMT is dissolved in 30~40ml ultrapure water, with magnetic stirrer it is uniform after be transferred in stainless steel cauldron, will be close
The reaction kettle of envelope is put into 8~12h of heat preservation, obtained green powder in 80~120 DEG C of electronics baking ovens and is cleaned with water and ethyl alcohol, then
It is dry in vacuum oven；
D, by prepared Ni (OH)2With MoS2/ RGO is fully ground in the agate mortar to being uniformly mixed, and is then set mixture
In tube furnace, in Ar/H24~6h is kept the temperature in mixed atmosphere under the conditions of 450~550 DEG C, prepares NPNi-MoS2/ RGO composite wood
Material.
2. a kind of nanoporous nickel-molybdenum disulfide/graphene composite material preparation method according to claim 1,
It is characterized in that, in step b, the product is ultrasonically treated, two kinds of substance contacts can be made sufficiently, prevent MoS2Reunite.
3. a kind of nanoporous nickel-molybdenum disulfide/graphene composite material preparation method according to claim 1,
It is characterized in that, in step d, the mixture is placed in Ar/H2It anneals in mixed gas, makes Ni (OH)2It is reduced into NPNi, is increased
Reciprocation in strong composite material between each ingredient.
4. nanoporous nickel-molybdenum disulfide/graphene composite material that the method according to claim 11 obtains, conduct
Catalyst carries out electro-chemical test, comprising the following steps:
A, first by 1.5~2.5mg NPNi-MoS2/ RGO catalyst fines are dispersed in 0.4~0.6ml water/isopropanol/naphthol solution
In, uniform dispersion liquid is made in then 20~40min of ultrasound, 20~40 μ l dispersant liquid drops is taken out on glass-carbon electrode, in room
The lower drying of temperature, obtains 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, with the NPNi-MoS2/ RGO composite material is tested on CHI660E electrochemical workstation as working electrode,
Polarization curve test carries out in the rotating disk electrode (r.d.e) that rotation speed is 2025rpm, in the potential relative to reversible hydrogen electrode
Scanning range is 0~-0.8V, and scanning speed is 5mV s-1；
It is -0.15~0.1V, scanning speed in the potential scan range relative to reversible hydrogen electrode when carrying out cyclic voltammetry
For 100mV s-1；
Current versus time curve test is the sweep time under the constant voltage for being -0.19V relative to the potential of reversible hydrogen electrode
For 30000s；
D, the NPNi-MoS of preparation2Catalyst of/RGO the composite material as evolving hydrogen reaction, onset potential 85mV, identical
Under current density, catalytic performance is better than with MoS made from condition2、MoS2/ RGO and NPNi-MoS2。
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| CN113926479B (en) * | 2020-07-13 | 2022-08-09 | 中国科学院上海硅酸盐研究所 | Potassium molybdenum sulfur/nickel nitride composite material and preparation method and application thereof |
| CN115874215A (en) * | 2021-09-27 | 2023-03-31 | 中国科学院福建物质结构研究所 | Molybdenum carbide-nickel hydroxide composite material and preparation method and application thereof |
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