CN107685150B - A kind of carbon-coated Ni & MoO of N doping2Superfine nanowire and its preparation method and application - Google Patents

A kind of carbon-coated Ni & MoO of N doping2Superfine nanowire and its preparation method and application Download PDF

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CN107685150B
CN107685150B CN201710735409.1A CN201710735409A CN107685150B CN 107685150 B CN107685150 B CN 107685150B CN 201710735409 A CN201710735409 A CN 201710735409A CN 107685150 B CN107685150 B CN 107685150B
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CN107685150A (en
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麦立强
刘熊
温波
郭瑞婷
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Wuhan University of Technology WUT
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0547—Nanofibres or nanotubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Abstract

The present invention relates to a kind of carbon-coated Ni&MoO of N doping2Superfine nanowire and its preparation method and application, the material can be used as the evolving hydrogen reaction elctro-catalyst of high activity, high stability, and array is grown on carbon cloth, and the nano wire is by Ni nano particle and MoO2Nano particle is embedded in the carbon-coating composition of N doping, and the diameter of the nano wire is 10~20nm, and length is 1~2 μm, and the specific surface area of the nano-material is 87.1m2g‑1, carbon-coating of the appearance in the presence of the N doping with protective effect.Excellent evolving hydrogen reaction catalytic activity and durability are shown when the beneficial effects of the present invention are: the present invention is as evolving hydrogen reaction material, are the potential application materials of high efficiency, inexpensive evolving hydrogen reaction elctro-catalyst.

Description

A kind of carbon-coated Ni & MoO of N doping2Superfine nanowire and preparation method thereof and Using
Technical field
The invention belongs to the energy and catalysis material field, and in particular to a kind of carbon-coated Ni&MoO of N doping2It is ultra-fine to receive Rice noodles and its preparation method and application, the material can be used as the evolving hydrogen reaction elctro-catalyst of high activity, high stability.
Background technique
With rapidly depleting for fossil energy and becoming increasingly conspicuous for environmental problem, hydrogen have been considered as most cleaning and most There is one of the energy of development potentiality.Hydrogen, but discharge and the ring of carbon dioxide are mainly commercially prepared by the vaporization of coal Border pollution problem is inevitable and ignores.Half-reaction of the evolving hydrogen reaction as electrolysis water is that one kind is able to produce high-purity hydrogen Pollution-free technology.Efficient evolving hydrogen reaction elctro-catalyst, which needs to meet, can accelerate cathode reaction and obtain under low overpotential Obtain the requirement of high current density.Noble metal platinum-base material is optimal evolving hydrogen reaction catalyst, but its low amount of storage, Gao Cheng This and poor stability strongly limit large-scale commercial applications application.Therefore, find a kind of abundance, there is high catalysis to live The non-noble metal-based catalysts material of property and stability is particularly important.
Molybdenum dioxide (MoO with distortion rutile structure2) material, there is high electronic conductance (8.8 × 10-5Ω· Cm) and excellent heat/chemical stability, extensive research has been obtained in catalysis, energy field.The Mo atom side of research discovery recently Edge and O atom edge are active site, but MoO2There are serious agglomerations and few active site, serious to limit Its evolving hydrogen reaction catalytic activity is made.In order to solve MoO2Agglomeration traits and obtain high catalytic activity, carbon coating, construct it is multiple Condensation material, doping etc. are a kind of effective strategies；Meanwhile one-dimensional nano line structural material leads to because it possesses one-dimensional electron-transport The advantages that road, more active sites and reduction are reunited, it is widely used in energy stores and conversion.Therefore, synthesis has The carbon coating molybdenum-base composite material of 1-dimention nano cable architecture is of great significance to efficient stable evolving hydrogen reaction catalyst is developed.
Summary of the invention
It is an object of the invention to: a kind of carbon-coated Ni&MoO of N doping is provided2The preparation method of superfine nanowire, institute Obtained nanowire composite has excellent evolving hydrogen reaction activity and stability.
The technical proposal adopted by the invention to solve the above technical problems is that: a kind of carbon-coated Ni&MoO of N doping2It is super Thin nano wire, array are grown on carbon cloth, and the nano wire is by Ni nano particle and MoO2Nano particle is embedded in nitrogen and mixes Miscellaneous carbon-coating composition, the diameter of the nano wire are 10~20nm, and length is 1~2 μm, the ratio table of the nano-material Area is 87.1m2g-1, carbon-coating of the appearance in the presence of the N doping with protective effect.
According to the above scheme, there are 3~5 layers of graphitization carbon-coating, the MoO for the Ni nano particle appearance2Nanometer There are 1~2 layer of carbon-coatings for grain appearance.
According to the above scheme, the size of the Ni nano particle is 8~15nm, MoO2The size of nano particle be 3~ 8nm。
The carbon-coated Ni&MoO of N doping2The preparation method of superfine nanowire, includes following steps:
1) Ammonium Molybdate Tetrahydrate, Nickelous nitrate hexahydrate and 2-methylimidazole are taken, is added sequentially in methanol solvate, is stirred To uniform solution；
2) step 1) acquired solution is transferred in reaction kettle, and is disposed vertically one block of carbon cloth wherein, in certain temperature Lower carry out solvent thermal reaction；
3) after being cooled to room temperature, the carbon cloth sample in step 2) reaction kettle is taken out, and wash, dry, is grown On carbon cloth, nickeliferous polymolybdote organic-inorganic nano line presoma；
4) presoma obtained by step 3) is subjected to low temperature precalcining, then calcines at high temperature, can be obtained and be grown in carbon On cloth, the carbon-coated Ni&MoO of N doping2Superfine nano wire material.
According to the above scheme, low temperature precalcining temperature described in step 4) is 280~300 DEG C, and calcination time is 1~2h, is forged Burning atmosphere is Ar/H2(volume ratio 95:5) atmosphere；Second step calcination temperature is 500~600 DEG C, and calcination time is 1~2h, is risen Warm rate is 3~5 DEG C of min-1。
According to the above scheme, Ammonium Molybdate Tetrahydrate dosage described in step 1) is 0.25~0.35g, Nickelous nitrate hexahydrate dosage For 0.15~0.25g, the dosage of 2-methylimidazole is 0.45~0.55g, and the dosage of methanol solvate is 40~50mL.
According to the above scheme, the size of the carbon cloth is 20.0mm × 30.0mm.
According to the above scheme, solvent thermal reaction temperature described in step 2) be 160~180 DEG C, the reaction time be 20~for 24 hours.
The carbon-coated Ni&MoO of the N doping2Application of the superfine nanowire as evolving hydrogen reaction elctro-catalyst.
The present invention coats Ni&MoO using on carbon cloth, nitrogen-doped carbon is grown in2In superfine nano wire material, MoO2, Ni and Synergistic effect between nitrogen-doped carbon three has obtained the electrocatalysis material of high evolving hydrogen reaction activity and stability.Wherein, Ni The evolving hydrogen reaction activity for considerably increasing Mo base carbon composite is introduced, while the graphitization journey of carbon can be improved in calcining Degree, improves the acid resistance of material.In addition, one-dimensional superfine nano cable architecture, the introducing of out-phase Ni metal and gradient temperature calcine plan Slightly, be conducive to the serious agglomeration phenomenon for avoiding Mo base carbon composite in high-temperature calcination, and reduce Mo sill size, show It writes and improves evolving hydrogen reaction catalytic activity.
The beneficial effects of the present invention are: being based on MoO2, Ni and nitrogen-doped carbon synergistic effect, by protection of reducing atmosphere and The method of gradient temperature calcining obtains being grown on carbon cloth, N doping carbon-coated Ni and MoO2The composite Nano of nano particle Wire material.Excellent evolving hydrogen reaction catalytic activity and durability are shown when the present invention is as evolving hydrogen reaction material, be high efficiency, The potential application material of inexpensive evolving hydrogen reaction elctro-catalyst.The carbon-coated Ni&MoO of N doping2Superfine nano wire material is in acid Property solution shows efficient and stable Hydrogen Evolution Performance, for acquisition -10mA cm-2Current density, overpotential be 50.0~ 60.0mV, Tafel slope are 41mV dec-1, and excellent stability is shown, after stability test 40000s, for acquisition- 10mA cm-2Current density, overpotential only increases as 73mV.Operation of the present invention is simple, used solvent-thermal method and gradient temperature It is low for equipment requirements to spend calcination method, is easy to large-scale production, has broad application prospects.
Detailed description of the invention
Fig. 1 is the carbon coating Ni&MoO of the embodiment of the present invention 12The synthesis schematic diagram of superfine nano wire material；
Fig. 2 is the scanning electron microscope of the nickeliferous polymolybdote organic-inorganic nano line presoma of the embodiment of the present invention 1 (SEM), transmission electron microscope (TEM) and selective electron diffraction (SAED) figure；
Fig. 3 is the XRD diagram of the nickeliferous polymolybdote organic-inorganic nano line presoma of the embodiment of the present invention 1；
Fig. 4 is the carbon coating Ni&MoO of the embodiment of the present invention 12The XRD diagram of superfine nano wire material；
Fig. 5 is the carbon coating Ni&MoO of the embodiment of the present invention 12The scanning electron microscope (SEM) photograph of superfine nano wire material；
Fig. 6 is the carbon coating Ni&MoO of the embodiment of the present invention 12The transmission electron microscope picture of superfine nano wire material；
Fig. 7 is the carbon coating Ni&MoO of the embodiment of the present invention 12The high-resolution-ration transmission electric-lens figure of superfine nano wire material；
Fig. 8 is the carbon coating Ni&MoO of the embodiment of the present invention 12The distribution diagram of element of superfine nano wire material；
Fig. 9 is the carbon coating Ni&MoO of the embodiment of the present invention 12The evolving hydrogen reaction catalytic activity of superfine nano wire material and steady Qualitative figure；
Figure 10 is the carbon coating Ni&MoO of the embodiment of the present invention 12Scanning after the circulation 40000s of superfine nano wire material Electron microscope；
Figure 11 is the carbon coating Ni&MoO of the embodiment of the present invention 12Transmission after the circulation 40000s of superfine nano wire material Electron microscope；
Figure 12 is the carbon coating Ni&MoO of the embodiment of the present invention 72The scanning electron microscope (SEM) photograph of superfine nano wire material；
Figure 13 is the carbon coating Ni&MoO of the embodiment of the present invention 82The scanning electron microscope (SEM) photograph of superfine nano wire material；
Figure 14 is the carbon coating Ni&MoO of the embodiment of the present invention 72The evolving hydrogen reaction catalytic activity of superfine nano wire material and Stability diagram；
Figure 15 is the carbon coating Ni&MoO of the embodiment of the present invention 82The evolving hydrogen reaction catalytic activity of superfine nano wire material and Stability diagram；
Specific embodiment
In order to better understand the present invention, below with reference to embodiment the present invention is furture elucidated content, but it is of the invention interior Appearance is not limited solely to the following examples.
Embodiment 1:
It is grown on carbon cloth, N doping carbon-coated Ni and MoO2The composite Nano wire material preparation side of nano particle Method includes the following steps:
1) 0.3g Ammonium Molybdate Tetrahydrate, 0.2g Nickelous nitrate hexahydrate and 0.5g 2-methylimidazole are taken first, are added sequentially to In the methanol solvate of 40mL, uniform solution is stirred to get；
2) step 1) acquired solution is transferred in 50mL reaction kettle, and be disposed vertically wherein one piece of 20.0mm × The carbon cloth of 30.0mm carries out solvent thermal reaction for 24 hours at 160 DEG C；
3) after being cooled to room temperature, the carbon cloth sample in step 2) reaction kettle is taken out, and respectively with deionized water, anhydrous Ethyl alcohol respectively washs 3 times, dries in 70 DEG C of vacuum ovens, obtains polymolybdote organic and inorganic be grown on carbon cloth, nickeliferous Nanowire precursor；
4) by the obtained product of step 3) in Ar/H2Gradient temperature calcining, first step calcining temperature are carried out under mixed atmosphere Degree is 280 DEG C, calcination time 2h, and heating rate is 5 DEG C of min-1, second step calcination temperature is 600 DEG C, calcination time 2h, Heating rate is 5 DEG C of min-1, obtain being grown on carbon cloth, N doping carbon-coated Ni and MoO2The composite Nano of nano particle Wire material.
As shown in Figure 1, synthesis mechanism of the invention is: using nickel ion, molybdenum acid ion and 2-methylimidazole in solvent Complexation reaction is carried out under heat condition and obtains polymolybdote organic-inorganic nano line presoma be grown on carbon cloth, nickeliferous, then Gradient temperature calcining is carried out to presoma under reducing atmosphere, finally synthesizes and a kind of is grown on carbon cloth, nitrogen-doped carbon cladding Ni&MoO2Superfine nano wire material；Design Mechanism of the invention are as follows: using carbon cloth as substrate, it is viscous to avoid insulating polymer Tie the use of agent, it is suppressed that nano wire in calcination process from reuniting, convenient for coming into full contact with for electrocatalysis material and electrolyte.Ni The introducing of simple substance promotes the formation of high graphitization carbon-coating, improves the catalytic activity, acidproof of electronic conductivity, electrocatalysis material Property and stability.Meanwhile MoO2, synergistic effect between Ni and nitrogen-doped carbon, significantly improve the evolving hydrogen reaction catalysis of material Activity.
With this example product production on carbon cloth, N doping carbon-coated Ni and MoO2The composite nano-line of nano particle For material, as shown in Figures 2 and 3, the nickeliferous polymolybdote organic-inorganic nano line presoma that solvent thermal reaction obtains is passed through SEM, TEM and XRD characterization, it can be seen that nano wire is uniform to be grown on carbon cloth, and nano wire has low-crystalline feature.Such as Shown in Fig. 4, by XRD spectrum, show to be grown on carbon cloth, N doping carbon-coated Ni and MoO2Nano particle it is compound Nano-material is MoO2With the compound phase of Ni, the diffraction maximum of carbon cloth is derived from~26 ° of broad peaks.As shown in figure 5, passing through SEM characterization, it can be seen that be grown on carbon cloth, N doping carbon-coated Ni and MoO2The composite Nano wire material of nano particle With uniform and complete nanowire structure.(Fig. 6) is schemed in conjunction with TEM, and the partial size of Ni nano particle is 8~15nm, MoO2Nanometer The partial size of particle is 3~8nm, and the diameter of nano wire is 10~20nm, by Ni and MoO2The composite nano-line of nano particle composition There are carbon coating layers for appearance, wherein as shown in fig. 7, there are 3~5 layers of graphitization carbon-coating, MoO for Ni nano particle appearance2Nanometer There are 1~2 layer of carbon-coatings for particle appearance.By transmission electron microscope distribution diagram of element (Fig. 8), show that the material contains Ni, Mo, C, N, O Element, Ni element domain of the existence is obvious and isolated, and Mo element is uniform to be distributed in entire nano wire.
The preparation of this example is grown on carbon cloth, N doping carbon-coated Ni and MoO2The composite nano-line of nano particle Material tests its electrocatalysis characteristic as evolving hydrogen reaction elctro-catalyst, using three electrode assemblies.Wherein, saturated calomel electrode conduct Reference electrode, coated graphite rod electrrode are used as the composite Nano wire material (having a size of 1cm × 1cm) being grown on carbon cloth to electrode to make For working electrode, test solution is 0.5M H2SO4.As shown in figure 9, the material shows excellent evolving hydrogen reaction activity and stablizes Property.For acquisition -10mA cm-2Current density, overpotential be~50mV；After stability test 40000s, for acquisition -10mA cm-2Current density, overpotential 75mV；After testing 80000s, for acquisition -20mA cm-2Current density, overpotential is 95.7mV.As shown in FIG. 10 and 11, it is grown on carbon cloth, N doping carbon-coated Ni and MoO2The composite Nano of nano particle Cable architecture is complete, and each component still exists.The above results show to be grown on carbon cloth, N doping carbon-coated Ni and MoO2 The composite Nano wire material of nano particle has excellent evolving hydrogen reaction activity and stability, is high-performance evolving hydrogen reaction catalyst Potential application material.
Embodiment 2:
1) 0.3g Ammonium Molybdate Tetrahydrate, 0.2g Nickelous nitrate hexahydrate and 0.5g 2-methylimidazole are taken, 40mL is added sequentially to Methanol solvate in, stir to get uniform solution；
2) step 1) acquired solution is transferred in 50mL reaction kettle, and be disposed vertically wherein one piece of 20.0mm × The carbon cloth of 30.0mm carries out solvent thermal reaction for 24 hours at 180 DEG C；
3) after being cooled to room temperature, the carbon cloth sample in step 2) reaction kettle is taken out, and respectively with deionized water, anhydrous Ethyl alcohol respectively washs 3 times, dries in 70 DEG C of vacuum ovens, obtains polymolybdote organic and inorganic be grown on carbon cloth, nickeliferous Nanowire precursor；
4) by the obtained product of step 3) in Ar/H2Gradient temperature calcining is carried out under atmosphere, first step calcination temperature is 280 DEG C, calcination time 2h, heating rate is 5 DEG C of min-1；Second step calcination temperature is 600 DEG C, calcination time 2h, heating Rate is 5 DEG C of min-1, obtain being grown on carbon cloth, N doping carbon-coated Ni and MoO2The composite Nano wire rod of nano particle Material.
On carbon cloth, N doping carbon-coated Ni and MoO is grown in so that the present embodiment is resulting2The compound of nano particle is received For nanowire material, for acquisition -10mA cm-2Current density, overpotential be~49.5mV；After stability test 40000s, it is Acquisition -10mA cm-2Current density, overpotential 73mV.
Embodiment 3:
1) 0.3g Ammonium Molybdate Tetrahydrate, 0.2g Nickelous nitrate hexahydrate and 0.5g 2-methylimidazole are taken, 40mL is added sequentially to Methanol solvate in, stir to get uniform solution；
2) step 1) acquired solution is transferred in 50mL reaction kettle, and be disposed vertically wherein one piece of 20.0mm × The carbon cloth of 30.0mm carries out solvent thermal reaction 20h at 160 DEG C；
3) after being cooled to room temperature, the carbon cloth sample in step 2) reaction kettle is taken out, and respectively with deionized water, anhydrous Ethyl alcohol respectively washs 3 times, dries in 70 DEG C of vacuum ovens, obtains polymolybdote organic and inorganic be grown on carbon cloth, nickeliferous Nanowire precursor；
4) by the obtained product of step 3) in Ar/H2Gradient temperature calcining is carried out under atmosphere, first step calcination temperature is 280 DEG C, calcination time 2h, heating rate is 5 DEG C of min-1；Second step calcination temperature is 600 DEG C, calcination time 2h, heating Rate is 5 DEG C of min-1, obtain being grown on carbon cloth, N doping carbon-coated Ni and MoO2The composite Nano wire rod of nano particle Material.
On carbon cloth, N doping carbon-coated Ni and MoO is grown in so that the present embodiment is resulting2The compound of nano particle is received For nanowire material, for acquisition -10mA cm-2Current density, overpotential be~52mV；After stability test 40000s, to obtain Obtain -10mA cm-2Current density, overpotential 75mV.
Embodiment 4:
1) 0.3g Ammonium Molybdate Tetrahydrate, 0.2g Nickelous nitrate hexahydrate and 0.5g 2-methylimidazole are taken, 40mL is added sequentially to Methanol solvate in, stir to get uniform solution；
2) step 1) acquired solution is transferred in 50mL reaction kettle, and be disposed vertically wherein one piece of 20.0mm × The carbon cloth of 30.0mm carries out solvent thermal reaction for 24 hours at 160 DEG C；
3) after being cooled to room temperature, the carbon cloth sample in step 2) reaction kettle is taken out, and respectively with deionized water, anhydrous Ethyl alcohol respectively washs 3 times, dries in 70 DEG C of vacuum ovens, obtains polymolybdote organic and inorganic be grown on carbon cloth, nickeliferous Nanowire precursor；
4) by the obtained product of step 3) in Ar/H2Gradient temperature calcining, first step calcining temperature are carried out under mixed atmosphere Degree is 280 DEG C, calcination time 2h, and heating rate is 5 DEG C of min-1；Second step calcination temperature is 600 DEG C, calcination time 1.5 H, heating rate are 5 DEG C of min-1, obtain being grown on carbon cloth, N doping carbon-coated Ni and MoO2The compound of nano particle is received Nanowire material.
On carbon cloth, N doping carbon-coated Ni and MoO is grown in so that the present embodiment is resulting2The compound of nano particle is received For nanowire material, to obtain 10mA cm-2Current density, overpotential be~54mV；After stability test 40000s, to obtain Obtain 10mA cm-2Current density, overpotential 72mV.
Embodiment 5:
1) 0.3g Ammonium Molybdate Tetrahydrate, 0.2g Nickelous nitrate hexahydrate and 0.5g 2-methylimidazole are taken, 40mL is added sequentially to Methanol solvate in, stir to get uniform solution；
2) step 1) acquired solution is transferred in 50mL reaction kettle, and be disposed vertically in a kettle one piece of 20.0mm × The carbon cloth of 30.0 mm carries out solvent thermal reaction for 24 hours at 160 DEG C；
3) after being cooled to room temperature, the carbon cloth sample in step 2) reaction kettle is taken out, and respectively with deionized water, anhydrous Ethyl alcohol respectively washs 3 times, dries in 70 DEG C of vacuum ovens, obtains polymolybdote organic and inorganic be grown on carbon cloth, nickeliferous Nanowire precursor；
4) by the obtained product of step 3) in Ar/H2Gradient temperature calcining is carried out under atmosphere, first step calcination temperature is 280 DEG C, calcination time 1h, heating rate is 5 DEG C of min-1；Second step calcination temperature is 600 DEG C, calcination time 1.5h, is risen Warm rate is 5 DEG C of min-1, obtain being grown on carbon cloth, N doping carbon-coated Ni and MoO2The composite nano-line of nano particle Material.
On carbon cloth, N doping carbon-coated Ni and MoO is grown in so that the present embodiment is resulting2The compound of nano particle is received For nanowire material, for acquisition -10mA cm-2Current density, overpotential be~53mV；After stability test 40000s, to obtain Obtain -10mA cm-2Current density, overpotential 70mV.
Embodiment 6:
1) 0.3g Ammonium Molybdate Tetrahydrate, 0.2g Nickelous nitrate hexahydrate and 0.5g 2-methylimidazole are taken, 40mL is added sequentially to Methanol solvate in, stir to get uniform solution；
2) step 1) acquired solution is transferred in 50mL reaction kettle, and be disposed vertically wherein one piece of 20.0mm × The carbon cloth of 30.0mm carries out solvent thermal reaction for 24 hours at 160 DEG C；
3) after being cooled to room temperature, the carbon cloth sample in step 2) reaction kettle is taken out, and respectively with deionized water, anhydrous Ethyl alcohol respectively washs 3 times, dries in 70 DEG C of vacuum ovens, obtains polymolybdote organic and inorganic be grown on carbon cloth, nickeliferous Nanowire precursor；
4) by the obtained product of step 3) in Ar/H2Gradient temperature calcining is carried out under atmosphere, first step calcination temperature is 300 DEG C, calcination time 2h, heating rate is 5 DEG C of min-1；Second step calcination temperature is 600 DEG C, calcination time 1.5h, is risen Warm rate is 5 DEG C of min-1, obtain being grown on carbon cloth, N doping carbon-coated Ni and MoO2The composite nano-line of nano particle Material.
On carbon cloth, N doping carbon-coated Ni and MoO is grown in so that the present embodiment is resulting2The compound of nano particle is received For nanowire material, for acquisition -10mA cm-2Current density, overpotential be~52mV；After stability test 40000s, to obtain Obtain -10mA cm-2Current density, overpotential 74mV.
Embodiment 7:
1) 0.3g Ammonium Molybdate Tetrahydrate, 0.2g Nickelous nitrate hexahydrate and 0.5g 2-methylimidazole are taken, 40mL is added sequentially to Methanol solvate in, stir to get uniform solution；
2) step 1) acquired solution is transferred in 50mL reaction kettle, and be disposed vertically wherein one piece of 20.0mm × The carbon cloth of 30.0mm carries out solvent thermal reaction for 24 hours at 160 DEG C；
3) after being cooled to room temperature, the carbon cloth sample in step 2) reaction kettle is taken out, and respectively with deionized water, anhydrous Ethyl alcohol respectively washs 3 times, dries in 70 DEG C of vacuum ovens, obtains polymolybdote organic and inorganic be grown on carbon cloth, nickeliferous Nanowire precursor；
4) by the obtained product of step 3) in Ar/H2Gradient temperature calcining is carried out under atmosphere, first step calcination temperature is 280 DEG C, calcination time 2h, heating rate is 5 DEG C of min-1；Second step calcination temperature is 500 DEG C, calcination time 2h, heating Rate is 5 DEG C of min-1, obtain being grown on carbon cloth, N doping carbon-coated Ni and MoO2The composite Nano wire rod of nano particle Material.
With this example product production on carbon cloth, N doping carbon-coated Ni and MoO2The composite nano-line of nano particle It for material, as shown in figure 12, is characterized by SEM, it can be seen that be grown on carbon cloth, N doping carbon-coated Ni and MoO2 The composite Nano wire material of nano particle has uniform and complete nanowire structure.
The preparation of this example is grown on carbon cloth, N doping carbon-coated Ni and MoO2The composite nano-line of nano particle Material tests its electrocatalysis characteristic as evolving hydrogen reaction elctro-catalyst, using three electrode assemblies.Wherein, saturated calomel electrode conduct Reference electrode, coated graphite rod electrrode are used as the composite Nano wire material (having a size of 1cm × 1cm) being grown on carbon cloth to electrode to make For working electrode, test solution is 0.5M H2SO4.As shown in figure 14, it is grown on carbon cloth, nitrogen with the present embodiment is resulting and mixes Miscellaneous carbon-coated Ni and MoO2For the composite Nano wire material of nano particle, for acquisition -10mA cm-2Current density, it is excessively electric Gesture is 101mV；After stability test 40000s, for acquisition -10mA cm-2Current density, overpotential 159mV.
Embodiment 8:
1) 0.3g Ammonium Molybdate Tetrahydrate, 0.2g Nickelous nitrate hexahydrate and 0.5g 2-methylimidazole are taken, 40mL is added sequentially to Methanol solvate in, stir to get uniform solution；
2) step 1) acquired solution is transferred in 50mL reaction kettle, and be disposed vertically wherein one piece of 20.0mm × The carbon cloth of 30.0mm carries out solvent thermal reaction for 24 hours at 160 DEG C；
3) after being cooled to room temperature, the carbon cloth sample in step 2) reaction kettle is taken out, and respectively with deionized water, anhydrous Ethyl alcohol respectively washs 3 times, dries in 70 DEG C of vacuum ovens, obtains polymolybdote organic and inorganic be grown on carbon cloth, nickeliferous Nanowire precursor；
4) by the obtained product of step 3) in Ar/H2Gradient temperature calcining is carried out under atmosphere, first step calcination temperature is 280 DEG C, calcination time 2h, heating rate is 5 DEG C of min-1；Second step calcination temperature is 550 DEG C, calcination time 2h, heating Rate is 5 DEG C of min-1, obtain being grown on carbon cloth, N doping carbon-coated Ni and MoO2The composite Nano wire rod of nano particle Material.
With this example product production on carbon cloth, N doping carbon-coated Ni and MoO2The composite nano-line of nano particle It for material, as shown in figure 13, is characterized by SEM, it can be seen that be grown on carbon cloth, N doping carbon-coated Ni and MoO2 The composite Nano wire material of nano particle has uniform and complete nanowire structure.
The preparation of this example is grown on carbon cloth, N doping carbon-coated Ni and MoO2The composite nano-line of nano particle Material tests its electrocatalysis characteristic as evolving hydrogen reaction elctro-catalyst, using three electrode assemblies.Wherein, saturated calomel electrode conduct Reference electrode, coated graphite rod electrrode are used as the composite Nano wire material (having a size of 1cm × 1cm) being grown on carbon cloth to electrode to make For working electrode, test solution is 0.5M H2SO4.As shown in figure 15, it is grown on carbon cloth, nitrogen with the present embodiment is resulting and mixes Miscellaneous carbon-coated Ni and MoO2For the composite Nano wire material of nano particle, for acquisition -10mA cm-2Current density, it is excessively electric Gesture is 67mV；After stability test 40000s, for acquisition -10mA cm-2Current density, overpotential 134mV.In conclusion On carbon cloth, N doping carbon-coated Ni and MoO is grown in by the way that embodiment 1,7,8 is resulting2The composite Nano of nano particle The comparison for the HER performance that wire material (high-temperature calcination temperature is respectively 500 DEG C, 550 DEG C, 600 DEG C) is tested, it can be seen that 600 Catalyst under DEG C calcination condition has optimal HER activity and stability, has certain application prospect.

Claims (9)

1. a kind of carbon-coated Ni&MoO of N doping2Superfine nanowire, array are grown on carbon cloth, and the nano wire is by Ni Nano particle and MoO2Nano particle is embedded in the carbon-coating composition of N doping, and the diameter of the nano wire is 10~20nm, long Degree is 1~2 μm, and the specific surface area of the nano-material is 87.1m2g-1, appearance exists, and there is the nitrogen of protective effect to mix Miscellaneous carbon-coating.
2. the carbon-coated Ni&MoO of N doping according to claim 12Superfine nanowire, it is characterised in that the Ni receives There are 3~5 layers of graphitization carbon-coating, the MoO for rice grain appearance2There are 1~2 layer of carbon-coatings for nano particle appearance.
3. the carbon-coated Ni&MoO of N doping according to claim 12Superfine nanowire, it is characterised in that the Ni receives The size of rice grain is 8~15nm, MoO2The size of nano particle is 3~8nm.
4. the carbon-coated Ni&MoO of N doping described in claim 12The preparation method of superfine nanowire, includes following steps:
1) Ammonium Molybdate Tetrahydrate, Nickelous nitrate hexahydrate and 2-methylimidazole are taken, is added sequentially in methanol solvate, is stirred to get One solution；
2) step 1) acquired solution is transferred in reaction kettle, and is disposed vertically one block of carbon cloth wherein, at a certain temperature into Row solvent thermal reaction；
3) after being cooled to room temperature, the carbon cloth sample in step 2) reaction kettle is taken out, and wash, dry, obtains being grown in carbon On cloth, nickeliferous polymolybdote organic-inorganic nano line presoma；
4) presoma obtained by step 3) is subjected to low temperature precalcining, then calcines at high temperature, can be obtained and be grown on carbon cloth , the carbon-coated Ni&MoO of N doping2Superfine nano wire material.
5. the carbon-coated Ni&MoO of N doping according to claim 42The preparation method of superfine nanowire, which is characterized in that Low temperature precalcining temperature described in step 4) is 280~300 DEG C, and calcination time is 1~2h, calcination atmosphere Ar/H2Atmosphere, Ar/H2Its volume ratio is 95:5；Second step calcination temperature is 500~600 DEG C, and calcination time is 1~2h, and heating rate is 3~5 ℃min-1。
6. the carbon-coated Ni&MoO of N doping according to claim 42The preparation method of superfine nanowire, which is characterized in that Ammonium Molybdate Tetrahydrate dosage described in step 1) is 0.25~0.35g, and Nickelous nitrate hexahydrate dosage is 0.15~0.25g, 2- first The dosage of base imidazoles is 0.45~0.55g, and the dosage of methanol solvate is 40~50mL.
7. the carbon-coated Ni&MoO of N doping according to claim 42The preparation method of superfine nanowire, which is characterized in that The size of the carbon cloth is 20.0mm × 30.0mm.
8. the carbon-coated Ni&MoO of N doping according to claim 42The preparation method of superfine nanowire, which is characterized in that Solvent thermal reaction temperature described in step 2) be 160~180 DEG C, the reaction time be 20~for 24 hours.
9. the carbon-coated Ni&MoO of N doping described in claim 12Superfine nanowire is answered as evolving hydrogen reaction elctro-catalyst With.
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