CN107164779A - It is a kind of to be carried on nickel molybdenum base bimetallic carbide of nickel foam and its preparation method and application - Google Patents

It is a kind of to be carried on nickel molybdenum base bimetallic carbide of nickel foam and its preparation method and application Download PDF

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CN107164779A
CN107164779A CN201710228484.9A CN201710228484A CN107164779A CN 107164779 A CN107164779 A CN 107164779A CN 201710228484 A CN201710228484 A CN 201710228484A CN 107164779 A CN107164779 A CN 107164779A
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nickel
foam
molybdenum base
carried
nickel foam
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CN107164779B (en
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杨化桂
俎梦杨
刘鹏飞
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East China University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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    • C25B11/031—Porous electrodes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1241—Metallic substrates
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • 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
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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Abstract

The invention discloses a kind of nickel molybdenum base bimetallic carbide for being carried on nickel foam and its preparation method and application.The present invention grows bimetallic carbide Mo by hydro-thermal and the method for high-temperature carburizing as carbon source respectively as nickel source and molybdenum source, and glucose using nickel nitrate and ammonium molybdate in nickel foam surface in situ6Ni6C.This method is easy to operate, and raw material is easy to get, and prepares with low cost, and reaction time is short, and repeatability is high.This material shows excellent Hydrogen Evolution Performance in electrocatalytic decomposition water field.In acidic electrolyte solution, its overpotential of hydrogen evolution is in 51mV, and current density is up to 8~12mA cm‑2, it is possible to keep steady operation 200 more than hour without substantially decay；Meanwhile, in alkaline electrolyte solution, its overpotential of hydrogen evolution is in 34mV, and current density can also reach 8~12mA cm‑2, it is possible to keep steady operation 300 more than hour without substantially decay.The present invention be carried on the nickel molybdenum base bimetallic carbide of nickel foam not only can directly as electrocatalytic hydrogen evolution working electrode, may be simultaneously used for the fields such as chlorine industry, electrolysis hydraulic art, solar energy electrolyzing water hydrogen manufacturing.

Description

It is a kind of be carried on nickel molybdenum base bimetallic carbide of nickel foam and preparation method thereof and Using
Technical field
The invention belongs to be carried on the nickel molybdenum base bimetallic carbide nanometer material of nickel foam, the material using hydro-thermal and High-temperature carburizing method is prepared from, and possesses excellent properties in terms of electrocatalytic hydrogen evolution, is led in other energy developments and environmental protection Domain also possesses potential application value.
Background technology
Energy problem has been one of ten big problems that human development is faced since nearly 50 years, and the energy is the thing of mankind's activity Matter basis, the development of human society be unable to do without the appearance of high-grade energy and the use of advanced energy technology.Meanwhile, positioned at the 4th Environmental problem equally also should not be underestimated.At present, the traditional energy such as coal, oil, natural gas still occupies in global energy Very important effect, but the reserves of these resources on earth are but very limited, and it is generally dirty along with serious environment Dye problem.In the world today, the development of the energy, the relation of the energy and environment is the whole world, whole mankind's questions of common interest, It is also the major issue of Chinese society economic development.In numerous energy, hydrogen is as a kind of clean energy resource, with very high A kind of combustion heat value, it is considered to be preferable energy carrier, can be efficiently converted into available effective energy without bringing ring Border problem.And water electrolysis hydrogen production be most have prospect, one of most clean hydrogen production process, but cause energy because overpotential of hydrogen evolution is too high Consumption increase, so liberation of hydrogen material of the exploitation with high activity improves the focus that hydrogen generation efficiency this problem is current study frontier Problem.It is traditional can effectively reduce the ideal electrode material predominantly precious metals pt of overpotential of hydrogen evolution, but Pt is on earth Store content very low and expensive, it is impossible to realize large-scale promote.Therefore, a kind of high catalytic activity of R and D And the low hydrogen-precipitating electrode of cost price has important theory significance and practical value.
Using hydro-thermal and the method for high-temperature carburizing in the growth nickel molybdenum base bimetallic carbonization of nickel foam surface in situ in the present invention Thing Mo6Ni6C is used as Electrocatalytic Activity for Hydrogen Evolution Reaction agent.This material is in synthesis, and process is easy, and the prices of raw materials are cheap and nontoxic, product Hydrogen Evolution Performance is good, in 0.5M H2SO4In aqueous electrolyte, when its overpotential of hydrogen evolution is in -51mV, current density is 10mA cm-2, and stable working condition can be kept to reach 200 more than hour；In 1.0M KOH aqueous electrolytes, serve as When current potential is -34mV, current density also can reach 10mA cm-2, and it is 300 small that stable working condition can be kept to reach When more than, be it is a kind of replace noble metal liberation of hydrogen relatively good material.
The content of the invention
In view of the foregoing, it is an object to provide the nickel molybdenum base bimetallic carbide and its system for being carried on nickel foam Preparation Method and application, preparation method are simple, and cost is low.Prepared nano material has relatively low liberation of hydrogen potential, with excellent Electrocatalytic hydrogen evolution performance.It is instrument that need not be complicated in building-up process, simple to operate, be conducive to large-scale commercial Application.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of Ni is in the molybdenum base bimetallic carbide of nickel foam, the molecular formula of the bimetallic carbide Mo6Ni6C, belongs to cubic system, uniform in the covering of foam nickel surface, and bar-shaped cluster is constituted with nano particle, particle size 30~ 100 nanometers, it is shaped as irregular spherical, bar-shaped cluster yardstick is 0.5~1.5 micron.
A kind of hydro-thermal and high-temperature carburizing method of the nickel molybdenum base bimetallic carbide for being carried on nickel foam, including following step Suddenly：
(1) by 0.2~0.6g Nickelous nitrate hexahydrates, the hydration ammonium heptamolybdates of 0.3~0.7g tetra- and 0.05~0.25g grapes Sugar is scattered in 10~50mL deionized waters, is placed in the steel bushing of polytetrafluoroethyllining lining, by the foam of 1~5 certain area Nickel is put into, and in an oven 2~10 hours of hydro-thermal under the conditions of 150~200 DEG C, is naturally cooled to after room temperature, is used deionized water Nickel foam is rinsed well, be placed in 60 DEG C of baking ovens dry it is stand-by；
(2) nickel foam after the drying that 1~5 step (1) obtains is taken to be placed in the quartzy Noah's ark in tube furnace, with 0.05~ 0.3L min-1Well-mixed carrier gas is passed through, 60~180min is reacted, naturally cools to room temperature；
The temperature of the tube furnace is 500~900 DEG C, and the carrier gas is the gaseous mixture of argon gas and hydrogen；
(3) quartzy Noah's ark is taken out, that is, obtains nickel molybdenum base bimetallic carbide Mo6Ni6C, belongs to cubic system, in nickel foam table Face covering is uniform, and bar-shaped cluster is constituted with nano particle, particle size at 30~100 nanometers, be shaped as it is irregular spherical, it is bar-shaped Cluster yardstick is 0.5~1.5 micron.
The application of above-mentioned nickel molybdenum base bimetallic carbide, mainly in terms of electrocatalytic decomposition water hydrogen manufacturing.
Above-mentioned application process is as follows：0.2~0.6 mole of every liter of every liter of aqueous sulfuric acid/0.5~1.5 mole potassium hydroxide The aqueous solution is electrolyte solution, the nickel molybdenum base bimetallic carbide Mo for being grown on foam nickel surface6Ni6C is used as work electricity Pole, by reference electrode of silver-silver chloride electrode, coated graphite rod electrrode be that to electrode, test temperature is 15~25 DEG C；In acidic electrolysis In matter solution, when its overpotential of hydrogen evolution is in -51mV, current density is 8~12mA cm-2, and steady-working state can be kept 200 more than hour；In alkaline electrolyte solution, when overpotential is -34mV, current density also can reach 8~12mA cm-2, and steady-working state 300 can be kept more than hour.
The beneficial effects of the present invention are：
(1) the nickel molybdenum base bimetallic carbide of nickel foam is carried on using simple hydro-thermal and the synthesis of high-temperature carburizing method Mo6Ni6C, synthetic method is simple, simple operation, mild condition, and target product purity is high, and safety non-toxic can be synthesized in high volume；
(2) the nickel molybdenum base bimetallic carbide Mo of nickel foam will be carried on6Ni6As a result C shows as Electrocatalytic Activity for Hydrogen Evolution Reaction agent It has preferable Hydrogen Evolution Performance and overpotential is relatively low.In acidic electrolyte solution, when its overpotential of hydrogen evolution is in -51mV, Current density is 8~12mA cm-2, and steady-working state 200 can be kept more than hour；In alkaline electrolyte solution, when When overpotential is -34mV, current density can reach 8~12mA cm-2, and steady-working state 300 can be kept more than hour；
(3) in preparation process, all reagents are commercial product, it is not necessary to further processing；
(4) synthetic method is simple, and obtained material is easy to application, is conducive to the popularization and application in industrialized production, may be used also It is used as the liberation of hydrogen material in the systems such as chlorine industry, electrolysis hydraulic art, solar energy electrolyzing water hydrogen manufacturing and electrochemistry hydrogen manufacturing.
Brief description of the drawings
Fig. 1 is that the nickel molybdenum base bimetallic carbide for being carried on nickel foam prepared by embodiment 1 is carried in nickel foam Digital photograph；
Fig. 2 is that the nickel molybdenum base bimetallic carbide prepared by embodiment 1 is carried on nickel foam as working electrode in acidity And the liberation of hydrogen linear scan curve in alkaline electrolyte solution；
Fig. 3 is that the nickel molybdenum base bimetallic carbide prepared by embodiment 1 is carried on nickel foam as working electrode in acidity And current density is -10mA cm in alkaline electrolyte solution-2When constant current curve map；
Fig. 4 is the X ray diffracting spectrum of the nickel molybdenum base bimetallic carbide prepared by embodiment 1；
Fig. 5 is the X-ray absorption fine structure near side (ns) spectrum of the nickel molybdenum base bimetallic carbide prepared by embodiment 1；
Fig. 6 is the R spaces collection of illustrative plates of the nickel molybdenum base bimetallic carbide prepared by embodiment 1；
Fig. 7 is the scanning electron microscopic picture of the nickel molybdenum base bimetallic carbide for being carried on nickel foam prepared by embodiment 1.
Embodiment
Below, in conjunction with the accompanying drawings and embodiments, specific embodiments of the present invention are further described in detail, but should not Limited the scope of the invention with this.
" scope " disclosed herein is in the form of lower and upper limit.Can be respectively one or more lower limits, and one Or multiple upper limits.Given range is defined by selecting a lower limit and a upper limit.Selected lower and upper limit limit The border of special scope is determined.All scopes that can be defined by this way are included and can be combined, i.e., any lower limit It can combine to form a scope with any upper limit.For example, listing 60-120 and 80-110 scope for special parameter, manage The scope solved as 60-110 and 80-120 is also what is expected.If in addition, the minimum zone value 1 and 2 listed, and if listed Maximum magnitude 3,4 and 5, then following scope can all expect：1-2,1-4,1-5,2-3,2-4 and 2-5.
In the present invention, unless otherwise indicated, number range " a-b " represents the breviary of any real combinings between a to b Represent, wherein a and b are real numbers.Such as number range " 0-5 " represents all to have listed herein complete between " 0-5 " Portion's real number, " 0-5 " is that the breviary of these combinations of values is represented.
In the present invention, if without particularly illustrating, all embodiments mentioned in this article and the side of being preferable to carry out Formula can be combined with each other to form new technical scheme.
In the present invention, if without particularly illustrating, all technical characteristics and preferred feature mentioned in this article can New technical scheme is formed to be combined with each other.
The present invention is specifically described below in conjunction with specific embodiment is preferable to carry out method, but it is to be understood that ability Field technique personnel can reasonably be become on the premise of the scope limited without departing substantially from claims to these embodiments Change, improve and be mutually combined, so as to obtain new specific implementation method, these are by changing, improveing and be mutually combined acquisition New embodiment is also included within protection scope of the present invention.
Embodiment 1
Step 1: being carried on the preparation of the nickel molybdenum base bimetallic carbide of nickel foam
By 0.4362g Ni (NO3)2 6H2O, 0.5191g (NH4)6Mo7O24·4H2O and 0.1g glucose adds 30mL In deionized water, ultrasound is uniformly dispersed for 30 minutes, and obtained mixed solution is placed in the steel bushing of polytetrafluoroethyllining lining, is put into 21 square centimeter of nickel foam, reacts 6 hours in 150 DEG C of baking oven, naturally cools to room temperature and later takes nickel foam Go out, and cleaned with deionized water, be placed in 60 DEG C of baking ovens and dry.Nickel foam after drying loads quartzy Noah's ark；By quartz Noah's ark is pushed into tube furnace central thermal zone position, and seals up ring flange；By hydrogen and argon gas (hydrogen after spinner flowmeter is measured Flow is 0.015L min-1, argon flow amount is 0.085L min-1) be sufficiently mixed after enter tube furnace；With 5 DEG C of min-1Speed Tube furnace is warming up to 700 DEG C, constant temperature processing 120min by rate；Then, room temperature is naturally cooled to, quartzy Noah's ark is taken out, that is, obtains It is carried on the nickel molybdenum base bimetallic carbide of nickel foam.
Step 2: performance characterization is tested
By the nickel molybdenum base bimetallic carbide for being carried on nickel foam directly as working electrode, electrochemical Characterization survey is carried out Examination.Pass through CHI660 electrochemical workstations, standard three electrode system, by the obtained nickel molybdenum base bimetallic carbon for being carried on nickel foam Compound electrode is placed in the potassium hydroxide aqueous solution of the sulfuric acid of 0.5 mol/L and 1.0 mol/Ls, is carried out using conventional method Liberation of hydrogen linear scan is tested.
Fig. 1 is the electronic photo of product, it can be seen that prepared nickel molybdenum base bimetallic carbide is fairly evenly loaded In foam nickel surface.
Fig. 2 is the nickel molybdenum base bimetallic carbide and contrast experiment's sample that are carried on nickel foam prepared by embodiment 1 It is used as the liberation of hydrogen linear scan curve of working electrode.Wherein：Curve 1 is to be carried on the nickel molybdenum of nickel foam prepared by embodiment 1 Bimetallic carbide is working electrode, and silver-silver chloride electrode is reference electrode, and graphite rod is that hydrogen saturation 0.5 is rubbed to electrode That/liter sulfuric acid and 1.0 mol/L potassium hydroxide solutions are electrolyte, and test temperature is 25 DEG C, sweep speed is 50 millivolts/ Linear scan curve under second test condition.Curve 2 is that commercialization Pt/C is carried on nickel foam as working electrode using in contrast experiment, Silver-silver chloride electrode is reference electrode, and graphite rod is to electrode, the mol/L sulfuric acid of hydrogen saturation 0.5 and 1.0 mol/L hydrogen Potassium oxide solution is electrolyte, and test temperature is 25 DEG C, and sweep speed is that the linear scan under 50 mv s test conditions is bent Line.Curve 3 is that blank nickel foam is working electrode using in contrast experiment, and silver-silver chloride electrode is reference electrode, graphite rod for pair Electrode, the mol/L sulfuric acid of hydrogen saturation 0.5 and 1.0 mol/L potassium hydroxide solutions are electrolyte, and test temperature is 25 DEG C, Sweep speed is the linear scan curve under 50 mv s test conditions.
As can be seen from Figure 2, in acid dielectric, the nickel molybdenum base bimetallic carbide of nickel foam is carried on as working electrode When overpotential of hydrogen evolution is -51mV, current density is 10mA cm-2；In alkaline dielectric, when overpotential is -34mV, electricity Current density also can reach 10mA cm-2, it was demonstrated that being carried on the nickel molybdenum base bimetallic carbide of nickel foam has outstanding electro-catalysis Hydrogen evolution activity.Blank nickel foam is working electrode when overpotential of hydrogen evolution is -382mV, and current density can be only achieved 10mA cm-2, This illustrates that the activity of electrocatalytic hydrogen evolution is derived from the prepared nickel molybdenum base bimetallic carbide for being carried on nickel foam.
It is electrochemical in CHI660 that Fig. 3 show the prepared nickel molybdenum base bimetallic carbide for being carried on nickel foam in embodiment 1 Learn the constant current curve tested on work station (Shanghai Chen Hua instrument company).Test condition：Three-electrode system, 0.5 mol/L Sulfuric acid and 1.0 mol/L solution are electrolyte solution, the nickel molybdenum base bimetallic for being carried on nickel foam prepared by embodiment 1 Carbide is working electrode, and silver-silver chloride electrode is reference electrode, and graphite rod is auxiliary electrode, and follow current is -10mA cm-2, the continued electrolysis time is 200 and 300 hours.It is can be seen that from Fig. 3 Dependence Results using the load prepared by the present invention In nickel foam nickel molybdenum base bimetallic carbide as working electrode current density be -10mA cm-2Lower constant current continued electrolysis 200 and 300 hours, overpotential of hydrogen evolution is respectively maintained at -70mV and -40mV or so without substantially decline.Prove using this The prepared nickel molybdenum base bimetallic carbide for being carried on nickel foam of invention has preferable stability as electrode.
Fig. 4 for from the nickel foam of preparation ultrasound get off the X ray diffracting spectrum of after drying powder, be identified as Mo6Ni6C.Sweep speed is 3 ° of min-1, scanning range is 36 °~79 ° of X ray diffracting spectrum.
Fig. 5 composes for the X-ray absorption fine structure near side (ns) of product.Wherein：Curve 1 is standard sample molybdenum powder, curve in a figures 2 be that curve 3 is standard sample molybdenum trioxide so that ultrasound is got off the powder after drying in nickel foam prepared by embodiment 1；b Curve 1 is standard sample nickel monoxide in figure, and curve 2 is so that ultrasound is got off by drying in nickel foam prepared by embodiment 1 Powder afterwards, curve 3 is standard sample nickel powder.
As shown in Figure 5, Mo6Ni6C Absorption Fine Structure near side (ns) spectrum it is similar with molybdenum powder and nickel powder, and with molybdenum trioxide and Nickel monoxide has relatively big difference.Illustrate its in valence state with differing larger with molybdenum trioxide and nickel monoxide on electronic structure, with molybdenum Powder is more close with nickel powder, is lower valency, it was demonstrated that its intrinsic metallicity.
Fig. 6 is the R spaces collection of illustrative plates of molybdenum element in product, is to carry out Fourier to the extension side of X-ray absorption fine structure spectroscopy Leaf transformation obtain, can qualitative analysis product microcosmic coordination information.Wherein：Curve 1 be with prepared by embodiment 1 in nickel foam surpass Sound gets off the powder after drying, and curve 2 is standard sample molybdenum powder.
By comparing curve in Fig. 6, Mo6Ni6The extension side Fourier transform results of molybdenum element are similar with molybdenum powder in C. Two curve existsAndNearby obvious appearance, illustrates tungsten oxide Mo6Ni6C coordination information and molybdenum powder more class Seemingly, predominantly molybdenum molybdenum key, this is also the basic reason of stability of material.
Fig. 7 is the scanning electron microscope (SEM) photograph of product, by observing sample topography, and material is uniform in the covering of foam nickel surface, to receive Rice grain constitutes bar-shaped cluster, and particle size is shaped as irregular spherical at 50 nanometers, and bar-shaped cluster yardstick is 1.0 microns.
Compared with existing electrocatalytic hydrogen evolution material preparation method, the present invention has advantages below：Building-up process is simple, former Material selection is extensive, with low cost, and electrocatalytic hydrogen evolution activity is high.
Embodiment 2
By 0.4362g Ni (NO3)2 6H2O, 0.5191g (NH4)6Mo7O24·4H2O and 0.1g are scattered in glucose and added Enter in 30mL deionized waters, ultrasound is uniformly dispersed for 30 minutes, and obtained mixed solution is placed in the firm set of polytetrafluoroethyllining lining It is interior, 21 square centimeter of nickel foam is put into, 6 hours are reacted in 150 DEG C of baking oven, naturally cooling to after room temperature will bubble Foam nickel takes out, and is cleaned with deionized water, is placed in 60 DEG C of baking ovens and dries.Nickel foam after drying loads quartzy Noah's ark； Quartzy Noah's ark is pushed into tube furnace central thermal zone position, and seals up ring flange；Hydrogen and argon gas are measured by spinner flowmeter (hydrogen flowing quantity is 0.015L min afterwards-1, argon flow amount is 0.085Lmin-1) be sufficiently mixed after enter tube furnace；With 5 DEG C of min-1 Speed tube furnace is warming up to 500 DEG C, constant temperature processing 120min；Then, room temperature is naturally cooled to, quartzy Noah's ark is taken out, i.e., Obtain being carried on the nickel molybdenum base bimetallic carbide of nickel foam.Feature and performance are similar to Example 1.
Embodiment 3
By 0.4362g Ni (NO3)2 6H2O, 0.5191g (NH4)6Mo7O24·4H2O and 0.1g are scattered in glucose and added Enter in 30mL deionized waters, ultrasound is uniformly dispersed for 30 minutes, and obtained mixed solution is placed in the firm set of polytetrafluoroethyllining lining It is interior, 21 square centimeter of nickel foam is put into, 6 hours are reacted in 150 DEG C of baking oven, naturally cooling to after room temperature will bubble Foam nickel takes out, and is cleaned with deionized water, is placed in 60 DEG C of baking ovens and dries.Nickel foam after drying loads quartzy Noah's ark； Quartzy Noah's ark is pushed into tube furnace central thermal zone position, and seals up ring flange；Hydrogen and argon gas are measured by spinner flowmeter (hydrogen flowing quantity is 0.015L min afterwards-1, argon flow amount is 0.085L min-1) be sufficiently mixed after enter tube furnace；With 5 DEG C of min-1Speed tube furnace is warming up to 900 DEG C, constant temperature processing 120min；Then, room temperature is naturally cooled to, quartzy Noah's ark is taken out, i.e., Obtain being carried on the nickel molybdenum base bimetallic carbide of nickel foam.Feature and performance are similar to Example 1.
Materials application obtained by the present invention is in electrocatalytic hydrogen evolution.Prepare the nickel molybdenum base bimetallic carbon being carried in nickel foam The three electrode test systems that compound is applied to electrocatalytic hydrogen evolution are carried out at normal temperatures and pressures, wherein using silver-silver chloride electricity Extremely reference electrode, graphite rod is to electrode, the mol/L sulfuric acid of hydrogen saturation 0.5 and 1.0 mol/L potassium hydroxide solutions For electrolyte, test temperature is 25 DEG C.Presently preferred embodiments of the present invention is the foregoing is only, it is all according to scope of the present invention patent The equivalent changes and modifications done, should all belong to the covering scope of the present invention.

Claims (4)

1. a kind of nickel molybdenum base bimetallic carbide for being carried on nickel foam, it is characterised in that the bimetallic carbide molecular formula For Mo6Ni6C, belongs to cubic system, uniform in the covering of foam nickel surface, constitutes bar-shaped cluster with nano particle, particle size is 30 ~100 nanometers, it is shaped as irregular spherical, bar-shaped cluster yardstick is 0.5~1.5 micron.
2. a kind of preparation method for the nickel molybdenum base bimetallic carbide for being carried on nickel foam, it is characterised in that comprise the following steps：
(1) by 0.2~0.6g Nickelous nitrate hexahydrates, the hydration ammonium heptamolybdates of 0.3~0.7g tetra- and 0.05~0.25g grape sugars Dissipate in 10~50mL deionized waters, be placed in the steel bushing of polytetrafluoroethyllining lining, the nickel foam of 1~5 certain area is put Enter, in an oven 2~10 hours of hydro-thermal under the conditions of 150~200 DEG C, naturally cool to after room temperature, will be steeped with deionized water Foam nickel is rinsed well, be placed in 60 DEG C of baking ovens dry it is stand-by；
(2) nickel foam after the drying that 1~5 step (1) obtains is taken to be placed in the quartzy Noah's ark in tube furnace, with 0.05~0.3L min-1Well-mixed carrier gas is passed through, 60~180min is reacted, naturally cools to room temperature；
The temperature of the tube furnace is 500~900 DEG C, and the carrier gas is the gaseous mixture of argon gas and hydrogen；
(3) quartzy Noah's ark is taken out, that is, obtains being carried on the nickel molybdenum base bimetallic carbide Mo of nickel foam6Ni6C, belongs to cubic system, It is uniform in the covering of foam nickel surface, bar-shaped cluster is constituted with nano particle, particle size is shaped as not advising at 30~100 nanometers Then spherical, bar-shaped cluster yardstick is 0.5~1.5 micron.
3. the application of the nickel molybdenum base bimetallic carbide for being carried on nickel foam described in claim 1, it is characterised in that described negative Being loaded in the nickel molybdenum base bimetallic carbide of nickel foam is used for electrocatalytic decomposition water hydrogen manufacturing.
4. application according to claim 3, it is characterised in that application process is as follows：0.2~0.6 mole of every liter of sulfuric acid water Every liter of solution/0.5~1.5 mole potassium hydroxide aqueous solution is electrolyte solution, the nickel molybdenum base for being grown on foam nickel surface Bimetallic carbide Mo6Ni6C as working electrode, by reference electrode of silver-silver chloride electrode, coated graphite rod electrrode be to electrode, Test temperature is 15~25 DEG C；In acidic electrolyte solution, when its overpotential of hydrogen evolution is in -51mV, current density be 8~ 12mA cm-2, and steady-working state 200 can be kept more than hour；In alkaline electrolyte solution, when overpotential is -34mV When, current density can reach 8~12mA cm-2, and steady-working state 300 can be kept more than hour.
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