CN107685150A - A kind of Ni ＆ MoO of nitrogen-doped carbon cladding2Superfine nanowire and its preparation method and application - Google Patents

A kind of Ni ＆ MoO of nitrogen-doped carbon cladding2Superfine nanowire and its preparation method and application Download PDF

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CN107685150A
CN107685150A CN201710735409.1A CN201710735409A CN107685150A CN 107685150 A CN107685150 A CN 107685150A CN 201710735409 A CN201710735409 A CN 201710735409A CN 107685150 A CN107685150 A CN 107685150A
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moo
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doped carbon
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CN107685150B (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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Abstract

The present invention relates to a kind of Ni＆MoO of nitrogen-doped carbon cladding2Superfine nanowire and its preparation method and application, the material can be grown on carbon cloth as the evolving hydrogen reaction elctro-catalyst of high activity, high stability, its array, and the nano wire is by Ni nano particles and MoO2Nano particle is embedded in the carbon-coating composition of N doping, and a diameter of 10~20nm of described nano wire, length is 1~2 μm, and the specific surface area of described nano-material is 87.1m2g‑1, carbon-coating of its appearance in the presence of the N doping with protective effect.The beneficial effects of the invention are as follows：Excellent evolving hydrogen reaction catalytic activity and durability are shown when the present invention is as evolving hydrogen reaction material, is high efficiency, the potential application material of inexpensive evolving hydrogen reaction elctro-catalyst.

Description

A kind of Ni ＆ MoO of nitrogen-doped carbon cladding2Superfine 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 Ni＆MoO of nitrogen-doped carbon cladding2It is ultra-fine to receive Rice noodles and its preparation method and application, the material can be as the evolving hydrogen reaction elctro-catalysts of high activity, high stability.
Background technology
With the quick consumption of fossil energy and becoming increasingly conspicuous for environmental problem, hydrogen have been considered as most cleaning and most There is one of energy of development potentiality.It is commercial that hydrogen, but discharge and the ring of carbon dioxide are mainly prepared by the vaporization of coal Border pollution problem is inevitable and ignores.Half-reaction of the evolving hydrogen reaction as electrolysis water, it is that one kind can produce high-purity hydrogen Pollution-free technology.Efficient evolving hydrogen reaction elctro-catalyst needs to meet to 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, obtained in catalysis, energy field widely studied.Research finds Mo atomic edges recently It is active site with O atom edge, but MoO2In the presence of serious agglomeration and few avtive spot, seriously limit Its evolving hydrogen reaction catalytic activity.In order to solve MoO2Agglomeration traits and obtain high catalytic activity, carbon coating, construct composite wood Material, doping etc. are a kind of effective strategies；Meanwhile one-dimensional nano line structural material because its possess one-dimensional electron propagation ducts, The advantages that more avtive spots and reduction are reunited, it is widely used in energy stores and conversion.Therefore, synthesis has one-dimensional The carbon coating molybdenum-base composite material of nano thread structure is significant to development efficient stable evolving hydrogen reaction catalyst.
The content of the invention
It is an object of the invention to：A kind of Ni＆MoO of nitrogen-doped carbon cladding is provided2The preparation method of superfine nanowire, institute Obtained nanowire composite has excellent evolving hydrogen reaction activity and stability.
Technical scheme is used by the present invention solves above-mentioned technical problem：A kind of Ni＆MoO of nitrogen-doped carbon cladding2It is super Thin nano wire, its array are grown on carbon cloth, and the nano wire is by Ni nano particles and MoO2Nano particle is embedded in nitrogen and mixed Miscellaneous carbon-coating composition, a diameter of 10~20nm of described nano wire, length are 1~2 μm, the ratio table of described nano-material Area is 87.1m2g-1, carbon-coating of its appearance in the presence of the N doping with protective effect.
By such scheme, there is 3~5 layers of graphitization carbon-coating, described MoO in described Ni nano particles appearance2Nanometer 1~2 layer of carbon-coating be present in grain appearance.
By such scheme, the size of described Ni nano particles is 8~15nm, MoO2The size of nano particle be 3~ 8nm。
The Ni＆MoO of nitrogen-doped carbon cladding2The 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 homogeneous solution；
2) step 1) resulting solution is transferred in reactor, 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) reactor is taken out, and washs, 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 calcined at high temperature, you can obtain being grown in carbon On cloth, nitrogen-doped carbon cladding Ni＆MoO2Superfine nano wire material.
By such scheme, the 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 calcining heat is 500~600 DEG C, and calcination time is 1~2h, is risen Warm speed is 3~5 DEG C of min-1。
By such scheme, the 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.
By such scheme, the size of described carbon cloth is 20.0mm × 30.0mm.
By such scheme, the solvent thermal reaction temperature described in step 2) is 160~180 DEG C, and the reaction time is 20~24h.
The Ni＆MoO of described nitrogen-doped carbon cladding2Application 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 Cooperative effect between nitrogen-doped carbon three, the electrocatalysis material of high evolving hydrogen reaction activity and stability is obtained.Wherein, Ni The evolving hydrogen reaction activity for considerably increasing Mo base carbon composites is introduced, while the graphitization journey of carbon can be improved in calcining Degree, improve the acid resistance of material.In addition, one-dimensional superfine nano cable architecture, the introducing of out-phase Ni metals and gradient temperature calcining plan Slightly, be advantageous to the serious agglomeration phenomenon for avoiding Mo bases carbon composite in high-temperature calcination, and reduce Mo sill sizes, show Write and improve evolving hydrogen reaction catalytic activity.
The beneficial effects of the invention are as follows：Based on MoO2, Ni and nitrogen-doped carbon cooperative effect, by protection of reducing atmosphere and The method of gradient temperature calcining obtains being grown in the Ni and MoO of nitrogen-doped carbon cladding on carbon cloth2The composite Nano of nano particle Wire material.The present invention as evolving hydrogen reaction material when show excellent evolving hydrogen reaction catalytic activity and durability, be high efficiency, The potential application material of inexpensive evolving hydrogen reaction elctro-catalyst.The Ni＆MoO of nitrogen-doped carbon cladding2Superfine nano wire material is in acid Property solutions display go out 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 show excellent stability, after stability test 40000s, for obtain- 10mA cm-2Current density, overpotential only increases as 73mV.Simple to operate, used solvent-thermal method and gradient temperature of the invention It is low for equipment requirements to spend calcination method, is easy to large-scale production, has broad application prospects.
Brief description of the drawings
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 SEM of the nickeliferous polymolybdote organic-inorganic nano line presoma of the embodiment of the present invention 1 (SEM), transmission electron microscope (TEM) and SEAD (SAED) figure；
Fig. 3 is the XRD 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 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；
Embodiment
In order to be better understood from the present invention, with reference to embodiment the present invention is furture elucidated content, but the present invention's is interior Appearance is not limited solely to the following examples.
Embodiment 1：
It is grown in the Ni and MoO of nitrogen-doped carbon cladding on carbon cloth2The composite Nano wire material preparation side of nano particle Method, comprise the following steps：
1) 0.3g Ammonium Molybdate Tetrahydrates, 0.2g Nickelous nitrate hexahydrates and 0.5g 2-methylimidazoles are taken first, are added sequentially to In 40mL methanol solvate, stirring obtains uniform solution；
2) step 1) resulting solution is transferred in 50mL reactors, and be disposed vertically wherein one piece of 20.0mm × 30.0mm carbon cloth, solvent thermal reaction 24h is carried out at 160 DEG C；
3) after being cooled to room temperature, the carbon cloth sample in step 2) reactor is taken out, and respectively with deionized water, anhydrous Ethanol respectively washing 3 times, dry in 70 DEG C of vacuum drying chambers, obtain polymolybdote organic and inorganic be grown on carbon cloth, nickeliferous Nanowire precursor；
4) by the product obtained by step 3) in Ar/H2Gradient temperature calcining, first step calcining temperature are carried out under mixed atmosphere Spend for 280 DEG C, calcination time 2h, heating rate is 5 DEG C of min-1, second step calcining heat is 600 DEG C, calcination time 2h, Heating rate is 5 DEG C of min-1, obtain being grown in Ni and MoO that on carbon cloth, nitrogen-doped carbon coats2The composite Nano of nano particle Wire material.
As shown in figure 1, the synthesis mechanism of the present 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 under reducing atmosphere to presoma, finally synthesizes and a kind of is grown on carbon cloth, nitrogen-doped carbon cladding Ni＆MoO2Superfine nano wire material；The present invention Design Mechanism be：Using carbon cloth as substrate, avoid insulating polymer and glue Tie the use of agent, it is suppressed that nano wire, from reuniting, is easy to fully contacting for electrocatalysis material and electrolyte in calcination process.Ni The introducing of simple substance, promote the formation of high graphitization carbon-coating, improve the catalytic activity, acidproof of electronic conductivity, electrocatalysis material Property and stability.Meanwhile MoO2, cooperative 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, nitrogen-doped carbon cladding Ni and MoO2The composite nano-line of nano particle Exemplified by material, as shown in Figures 2 and 3, the nickeliferous polymolybdote organic-inorganic nano line presoma obtained to solvent thermal reaction passes through SEM, TEM and XRD are characterized, it can be seen that nano wire is homogeneous to be grown on carbon cloth, and nano wire has low-crystalline feature.Such as figure Shown in 4, by XRD spectrum, show to be grown in the Ni and MoO of nitrogen-doped carbon cladding on carbon cloth2The composite Nano of nano particle Wire material is MoO2With Ni compound phase, the diffraction maximum of carbon cloth is derived from~26 ° of broad peaks.As shown in figure 5, pass through SEM tables Sign, it can be seen that be grown in the Ni and MoO of nitrogen-doped carbon cladding on carbon cloth2The composite Nano wire material of nano particle has Homogeneous and complete nano thread structure.Scheme (Fig. 6) with reference to TEM, the particle diameter of Ni nano particles is 8~15nm, MoO2Nano particle Particle diameter be 3~8nm, a diameter of 10~20nm of nano wire, by Ni and MoO2The composite nano-line appearance of nano particle composition Carbon coating layer be present, wherein, as shown in fig. 7,3~5 layers of graphitization carbon-coating, MoO be present in Ni nano particles appearance2Outside nano particle 1~2 layer of carbon-coating be present in table.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 elements are homogeneous to be distributed in whole nano wire.
Prepared by this example is grown in the Ni and MoO of nitrogen-doped carbon cladding on carbon cloth2The 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 to electrode, and the composite Nano wire material being grown on carbon cloth (size is 1cm × 1cm) is made For working electrode, test solution is 0.5M H2SO4.As shown in figure 9, the material shows excellent evolving hydrogen reaction activity and stably Property.For acquisition -10mA cm-2Current density, overpotential is~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, the Ni and MoO of nitrogen-doped carbon cladding on carbon cloth are grown in2The composite Nano of nano particle Cable architecture is complete, and each component is still present.The above results show, are grown in the Ni and MoO of nitrogen-doped carbon cladding on carbon cloth2 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 Tetrahydrates, 0.2g Nickelous nitrate hexahydrates and 0.5g 2-methylimidazoles are taken, is added sequentially to 40mL Methanol solvate in, stirring obtain uniform solution；
2) step 1) resulting solution is transferred in 50mL reactors, and be disposed vertically wherein one piece of 20.0mm × 30.0mm carbon cloth, solvent thermal reaction 24h is carried out at 180 DEG C；
3) after being cooled to room temperature, the carbon cloth sample in step 2) reactor is taken out, and respectively with deionized water, anhydrous Ethanol respectively washing 3 times, dry in 70 DEG C of vacuum drying chambers, obtain polymolybdote organic and inorganic be grown on carbon cloth, nickeliferous Nanowire precursor；
4) by the product obtained by step 3) in Ar/H2Gradient temperature calcining is carried out under atmosphere, first step calcining heat is 280 DEG C, calcination time 2h, heating rate is 5 DEG C of min-1；Second step calcining heat is 600 DEG C, calcination time 2h, heating Speed is 5 DEG C of min-1, obtain being grown in Ni and MoO that on carbon cloth, nitrogen-doped carbon coats2The composite Nano wire rod of nano particle Material.
With the Ni and MoO that are grown in nitrogen-doped carbon cladding on carbon cloth obtained by the present embodiment2The compound of nano particle is received Exemplified by nanowire material, for acquisition -10mA cm-2Current density, overpotential is~49.5mV；After stability test 40000s, it is Acquisition -10mA cm-2Current density, overpotential 73mV.
Embodiment 3：
1) 0.3g Ammonium Molybdate Tetrahydrates, 0.2g Nickelous nitrate hexahydrates and 0.5g 2-methylimidazoles are taken, is added sequentially to 40mL Methanol solvate in, stirring obtain uniform solution；
2) step 1) resulting solution is transferred in 50mL reactors, and be disposed vertically wherein one piece of 20.0mm × 30.0mm carbon cloth, solvent thermal reaction 20h is carried out at 160 DEG C；
3) after being cooled to room temperature, the carbon cloth sample in step 2) reactor is taken out, and respectively with deionized water, anhydrous Ethanol respectively washing 3 times, dry in 70 DEG C of vacuum drying chambers, obtain polymolybdote organic and inorganic be grown on carbon cloth, nickeliferous Nanowire precursor；
4) by the product obtained by step 3) in Ar/H2Gradient temperature calcining is carried out under atmosphere, first step calcining heat is 280 DEG C, calcination time 2h, heating rate is 5 DEG C of min-1；Second step calcining heat is 600 DEG C, calcination time 2h, heating Speed is 5 DEG C of min-1, obtain being grown in Ni and MoO that on carbon cloth, nitrogen-doped carbon coats2The composite Nano wire rod of nano particle Material.
With the Ni and MoO that are grown in nitrogen-doped carbon cladding on carbon cloth obtained by the present embodiment2The compound of nano particle is received Exemplified by nanowire material, for acquisition -10mA cm-2Current density, overpotential is~52mV；After stability test 40000s, to obtain Obtain -10mA cm-2Current density, overpotential 75mV.
Embodiment 4：
1) 0.3g Ammonium Molybdate Tetrahydrates, 0.2g Nickelous nitrate hexahydrates and 0.5g 2-methylimidazoles are taken, is added sequentially to 40mL Methanol solvate in, stirring obtain uniform solution；
2) step 1) resulting solution is transferred in 50mL reactors, and be disposed vertically wherein one piece of 20.0mm × 30.0mm carbon cloth, solvent thermal reaction 24h is carried out at 160 DEG C；
3) after being cooled to room temperature, the carbon cloth sample in step 2) reactor is taken out, and respectively with deionized water, anhydrous Ethanol respectively washing 3 times, dry in 70 DEG C of vacuum drying chambers, obtain polymolybdote organic and inorganic be grown on carbon cloth, nickeliferous Nanowire precursor；
4) by the product obtained by step 3) in Ar/H2Gradient temperature calcining, first step calcining temperature are carried out under mixed atmosphere Spend for 280 DEG C, calcination time 2h, heating rate is 5 DEG C of min-1；Second step calcining heat is 600 DEG C, and calcination time is 1.5h, heating rate are 5 DEG C of min-1, obtain being grown in Ni and MoO that on carbon cloth, nitrogen-doped carbon coats2Nano particle is answered Close nano-material.
With the Ni and MoO that are grown in nitrogen-doped carbon cladding on carbon cloth obtained by the present embodiment2The compound of nano particle is received Exemplified by nanowire material, to obtain 10mA cm-2Current density, overpotential is~54mV；After stability test 40000s, to obtain Obtain 10mA cm-2Current density, overpotential 72mV.
Embodiment 5：
1) 0.3g Ammonium Molybdate Tetrahydrates, 0.2g Nickelous nitrate hexahydrates and 0.5g 2-methylimidazoles are taken, is added sequentially to 40mL Methanol solvate in, stirring obtain uniform solution；
2) step 1) resulting solution is transferred in 50mL reactors, and be disposed vertically in a kettle one piece of 20.0mm × 30.0mm carbon cloth, solvent thermal reaction 24h is carried out at 160 DEG C；
3) after being cooled to room temperature, the carbon cloth sample in step 2) reactor is taken out, and respectively with deionized water, anhydrous Ethanol respectively washing 3 times, dry in 70 DEG C of vacuum drying chambers, obtain polymolybdote organic and inorganic be grown on carbon cloth, nickeliferous Nanowire precursor；
4) by the product obtained by step 3) in Ar/H2Gradient temperature calcining is carried out under atmosphere, first step calcining heat is 280 DEG C, calcination time 1h, heating rate is 5 DEG C of min-1；Second step calcining heat is 600 DEG C, calcination time 1.5h, is risen Warm speed is 5 DEG C of min-1, obtain being grown in Ni and MoO that on carbon cloth, nitrogen-doped carbon coats2The composite nano-line of nano particle Material.
With the Ni and MoO that are grown in nitrogen-doped carbon cladding on carbon cloth obtained by the present embodiment2The compound of nano particle is received Exemplified by nanowire material, for acquisition -10mA cm-2Current density, overpotential is~53mV；After stability test 40000s, to obtain Obtain -10mA cm-2Current density, overpotential 70mV.
Embodiment 6：
1) 0.3g Ammonium Molybdate Tetrahydrates, 0.2g Nickelous nitrate hexahydrates and 0.5g 2-methylimidazoles are taken, is added sequentially to 40mL Methanol solvate in, stirring obtain uniform solution；
2) step 1) resulting solution is transferred in 50mL reactors, and be disposed vertically wherein one piece of 20.0mm × 30.0mm carbon cloth, solvent thermal reaction 24h is carried out at 160 DEG C；
3) after being cooled to room temperature, the carbon cloth sample in step 2) reactor is taken out, and respectively with deionized water, anhydrous Ethanol respectively washing 3 times, dry in 70 DEG C of vacuum drying chambers, obtain polymolybdote organic and inorganic be grown on carbon cloth, nickeliferous Nanowire precursor；
4) by the product obtained by step 3) in Ar/H2Gradient temperature calcining is carried out under atmosphere, first step calcining heat is 300 DEG C, calcination time 2h, heating rate is 5 DEG C of min-1；Second step calcining heat is 600 DEG C, calcination time 1.5h, is risen Warm speed is 5 DEG C of min-1, obtain being grown in Ni and MoO that on carbon cloth, nitrogen-doped carbon coats2The composite nano-line of nano particle Material.
With the Ni and MoO that are grown in nitrogen-doped carbon cladding on carbon cloth obtained by the present embodiment2The compound of nano particle is received Exemplified by nanowire material, for acquisition -10mA cm-2Current density, overpotential is~52mV；After stability test 40000s, to obtain Obtain -10mA cm-2Current density, overpotential 74mV.
Embodiment 7：
1) 0.3g Ammonium Molybdate Tetrahydrates, 0.2g Nickelous nitrate hexahydrates and 0.5g 2-methylimidazoles are taken, is added sequentially to 40mL Methanol solvate in, stirring obtain uniform solution；
2) step 1) resulting solution is transferred in 50mL reactors, and be disposed vertically wherein one piece of 20.0mm × 30.0mm carbon cloth, solvent thermal reaction 24h is carried out at 160 DEG C；
3) after being cooled to room temperature, the carbon cloth sample in step 2) reactor is taken out, and respectively with deionized water, anhydrous Ethanol respectively washing 3 times, dry in 70 DEG C of vacuum drying chambers, obtain polymolybdote organic and inorganic be grown on carbon cloth, nickeliferous Nanowire precursor；
4) by the product obtained by step 3) in Ar/H2Gradient temperature calcining is carried out under atmosphere, first step calcining heat is 280 DEG C, calcination time 2h, heating rate is 5 DEG C of min-1；Second step calcining heat is 500 DEG C, calcination time 2h, heating Speed is 5 DEG C of min-1, obtain being grown in Ni and MoO that on carbon cloth, nitrogen-doped carbon coats2The composite Nano wire rod of nano particle Material.
With this example product production on carbon cloth, nitrogen-doped carbon cladding Ni and MoO2The composite nano-line of nano particle Exemplified by material, as shown in figure 12, characterized by SEM, it can be seen that be grown in the Ni and MoO of nitrogen-doped carbon cladding on carbon cloth2 The composite Nano wire material of nano particle has homogeneous and complete nano thread structure.
Prepared by this example is grown in the Ni and MoO of nitrogen-doped carbon cladding on carbon cloth2The 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 to electrode, and the composite Nano wire material being grown on carbon cloth (size is 1cm × 1cm) is made For working electrode, test solution is 0.5M H2SO4.As shown in figure 14, mixed with the carbon cloth, nitrogen that is grown in obtained by the present embodiment The Ni and MoO of miscellaneous carbon coating2Exemplified by 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 Tetrahydrates, 0.2g Nickelous nitrate hexahydrates and 0.5g 2-methylimidazoles are taken, is added sequentially to 40mL Methanol solvate in, stirring obtain uniform solution；
2) step 1) resulting solution is transferred in 50mL reactors, and be disposed vertically wherein one piece of 20.0mm × 30.0mm carbon cloth, solvent thermal reaction 24h is carried out at 160 DEG C；
3) after being cooled to room temperature, the carbon cloth sample in step 2) reactor is taken out, and respectively with deionized water, anhydrous Ethanol respectively washing 3 times, dry in 70 DEG C of vacuum drying chambers, obtain polymolybdote organic and inorganic be grown on carbon cloth, nickeliferous Nanowire precursor；
4) by the product obtained by step 3) in Ar/H2Gradient temperature calcining is carried out under atmosphere, first step calcining heat is 280 DEG C, calcination time 2h, heating rate is 5 DEG C of min-1；Second step calcining heat is 550 DEG C, calcination time 2h, heating Speed is 5 DEG C of min-1, obtain being grown in Ni and MoO that on carbon cloth, nitrogen-doped carbon coats2The composite Nano wire rod of nano particle Material.
With this example product production on carbon cloth, nitrogen-doped carbon cladding Ni and MoO2The composite nano-line of nano particle Exemplified by material, as shown in figure 13, characterized by SEM, it can be seen that be grown in the Ni and MoO of nitrogen-doped carbon cladding on carbon cloth2 The composite Nano wire material of nano particle has homogeneous and complete nano thread structure.
Prepared by this example is grown in the Ni and MoO of nitrogen-doped carbon cladding on carbon cloth2The 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 to electrode, and the composite Nano wire material being grown on carbon cloth (size is 1cm × 1cm) is made For working electrode, test solution is 0.5M H2SO4.As shown in figure 15, mixed with the carbon cloth, nitrogen that is grown in obtained by the present embodiment The Ni and MoO of miscellaneous carbon coating2Exemplified by 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 summary, Being grown in as obtained by embodiment 1,7,8 is on carbon cloth, the Ni and MoO of nitrogen-doped carbon cladding2The composite Nano of nano particle The contrast for the HER performances 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 1. Ni＆MoO of nitrogen-doped carbon cladding2Superfine nanowire, its 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 a diameter of 10~20nm of described nano wire is long Spend for 1~2 μm, the specific surface area of described nano-material is 87.1m2g-1, its appearance is present mixes with the nitrogen of protective effect Miscellaneous carbon-coating.
  2. 2. the Ni＆MoO of nitrogen-doped carbon cladding according to claim 12Superfine nanowire, it is characterised in that described Ni receives 3~5 layers of graphitization carbon-coating, described MoO be present in rice grain appearance21~2 layer of carbon-coating be present in nano particle appearance.
  3. 3. the Ni＆MoO of nitrogen-doped carbon cladding according to claim 12Superfine nanowire, it is characterised in that described Ni receives The size of rice grain is 8~15nm, MoO2The size of nano particle is 3~8nm.
  4. 4. the Ni＆MoO of the nitrogen-doped carbon cladding 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, stirring obtains One solution；
    2) step 1) resulting solution is transferred in reactor, and is disposed vertically one block of carbon cloth wherein, entered at a certain temperature Row solvent thermal reaction；
    3) after being cooled to room temperature, the carbon cloth sample in step 2) reactor is taken out, and washs, 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 calcined at high temperature, you can obtain being grown on carbon cloth , nitrogen-doped carbon cladding Ni＆MoO2Superfine nano wire material.
  5. 5. the Ni＆MoO of nitrogen-doped carbon cladding according to claim 42The preparation method of superfine nanowire, it is characterised in that Low temperature precalcining temperature described in step 4) is 280~300 DEG C, and calcination time is 1~2h, calcination atmosphere Ar/H2(volume ratio For 95:5) atmosphere；Second step calcining heat is 500~600 DEG C, and calcination time is 1~2h, and heating rate is 3~5 DEG C of min-1。
  6. 6. the Ni＆MoO of nitrogen-doped carbon cladding according to claim 42The preparation method of superfine nanowire, it is characterised 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. 7. the Ni＆MoO of nitrogen-doped carbon cladding according to claim 42The preparation method of superfine nanowire, it is characterised in that The size of described carbon cloth is 20.0mm × 30.0mm.
  8. 8. the Ni＆MoO of nitrogen-doped carbon cladding according to claim 42The preparation method of superfine nanowire, it is characterised in that Solvent thermal reaction temperature described in step 2) is 160~180 DEG C, and the reaction time is 20~24h.
  9. 9. the Ni＆MoO of the nitrogen-doped carbon cladding described in claim 12Superfine nanowire should as evolving hydrogen reaction elctro-catalyst With.
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