CN107164779B - A kind of nickel molybdenum base bimetallic carbide and its preparation method and application being carried on nickel foam - Google Patents
A kind of nickel molybdenum base bimetallic carbide and its preparation method and application being carried on nickel foam Download PDFInfo
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- CN107164779B CN107164779B CN201710228484.9A CN201710228484A CN107164779B CN 107164779 B CN107164779 B CN 107164779B CN 201710228484 A CN201710228484 A CN 201710228484A CN 107164779 B CN107164779 B CN 107164779B
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
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- 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
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- 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
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- 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
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
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Abstract
The invention discloses a kind of nickel molybdenum base bimetallic carbide and its preparation method and application for being carried on nickel foam.The present invention uses nickel nitrate and ammonium molybdate, as carbon source, to grow bimetallic carbide Mo in nickel foam surface in situ by hydro-thermal and the method for high-temperature carburizing respectively as nickel source and molybdenum source and glucose6Ni6C.This method is easy to operate, and raw material is easy to get, and preparation cost is cheap, 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, for overpotential of hydrogen evolution in -51mV, current density is up to 8~12mA cm‑2, and steady operation 200 can be kept more than hour to decay without obvious；Meanwhile in alkaline electrolyte solution, for overpotential of hydrogen evolution in -34mV, current density also can achieve 8~12mA cm‑2, and steady operation 300 can be kept more than hour to decay without obvious.The nickel molybdenum base bimetallic carbide for being carried on nickel foam of the invention not only can may be simultaneously used for the fields such as chlorine industry, electrolysis hydraulic art, solar energy electrolyzing water hydrogen manufacturing directly as the working electrode of electrocatalytic hydrogen evolution.
Description
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, and has excellent properties in terms of electrocatalytic hydrogen evolution, leads in other energy developments and environmental protection
Domain also has potential application value.
Background technique
Energy problem has been one of the ten big problems that human development is faced since nearly 50 years, and the energy is the object 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 being located at the 4th
Environmental problem equally also should not be underestimated.Currently, the traditional energies such as coal, petroleum, natural gas still occupy in global energy
Very important effect, but the reserves of these resources on earth are very limited, and usually dirty along with serious environment
Dye problem.In the world today, the development of the energy, the relationship 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 has very high as a kind of clean energy resource
Combustion heat value, it is considered to be a kind of ideal energy carrier can be efficiently converted into available effective energy without bringing ring
Border problem.And water electrolysis hydrogen production is that most have one of prospect, most clean hydrogen production process, but lead to energy since overpotential of hydrogen evolution is excessively high
Consumption increases, so exploitation has the liberation of hydrogen material of high activity to improve the hot spot that hydrogen generation efficiency this project is current study frontier
Problem.Traditional ideal electrode material that can effectively reduce overpotential of hydrogen evolution is mainly precious metals pt, but Pt is on earth
It is very low and expensive to store content, cannot achieve large-scale popularization.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.
It is carbonized using hydro-thermal and the method for high-temperature carburizing in nickel foam surface in situ growth nickel molybdenum base bimetallic in the present invention
Object Mo6Ni6C is as Electrocatalytic Activity for Hydrogen Evolution Reaction agent.For this material in synthesis, 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 10mA
cm-2, and be able to maintain stable working condition and it is more than hour to reach 200；In 1.0M KOH aqueous electrolyte, serve as
When current potential is -34mV, current density also can reach 10mA cm-2, and be able to maintain stable working condition and reach 300 small
When more than, be it is a kind of replace noble metal liberation of hydrogen relatively good material.
Summary 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 is simple, at low cost.Prepared nano material has lower liberation of hydrogen potential, has excellent
Electrocatalytic hydrogen evolution performance.Complicated instrument, easy to operate is not needed in synthesis process, is conducive to large-scale industrial application.
To achieve the above object, the present invention adopts the following technical scheme:
In the molybdenum base bimetallic carbide of nickel foam, the molecular formula of the bimetallic carbide is for a kind of nickel load
Mo6Ni6C belongs to cubic system, the covering of foam nickel surface uniformly, rodlike cluster is formed with nano particle, particle size 30~
100 nanometers, for shape to be irregular spherical, rodlike cluster scale is 0.5~1.5 micron.
A kind of hydro-thermal and high-temperature carburizing method of the nickel molybdenum base bimetallic carbide being carried on nickel foam, including walk as follows
It is rapid:
(1) by 0.2~0.6g Nickelous nitrate hexahydrate, 0.3~0.7g tetra- is hydrated ammonium heptamolybdate and 0.05~0.25g grape
Sugar is scattered in 10~50mL deionized water, is placed in the steel bushing of polytetrafluoroethyllining lining, by the foam of 1~5 certain area
Nickel is put into, in an oven 2~10 hours of hydro-thermal under the conditions of 150~200 DEG C, after cooled to room temperature, uses deionized water
Nickel foam is rinsed well, is placed in 60 DEG C of baking ovens and dries for use；
(2) nickel foam is placed in the quartzy Noah's ark in tube furnace after the drying for taking 1~5 step (1) to obtain, with 0.05~
0.3L min-1It is passed through well-mixed carrier gas, reacts 60~180min, cooled 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 to get nickel molybdenum base bimetallic carbide Mo is arrived6Ni6C belongs to cubic system, in nickel foam table
Face covering uniformly, with nano particle forms rodlike cluster, and for particle size at 30~100 nanometers, shape is rodlike to be irregular spherical
Cluster scale 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 method 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
Aqueous solution is electrolyte solution, the nickel molybdenum base bimetallic carbide Mo for being grown on foam nickel surface6Ni6C is as work electricity
Pole is to electrode by reference electrode, coated graphite rod electrrode of silver-silver chloride electrode, and 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 more than hour can be kept.
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, operates convenient, mild condition, and target product purity is high is safe and non-toxic, can in high volume synthesize；
(2) the nickel molybdenum base bimetallic carbide Mo of nickel foam will be carried on6Ni6C is as Electrocatalytic Activity for Hydrogen Evolution Reaction agent, the results showed that
Its with preferable Hydrogen Evolution Performance and overpotential it is lower.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 more than hour can be kept；In alkaline electrolyte solution, when
When overpotential is -34mV, current density can reach 8~12mA cm-2, and steady-working state 300 more than hour can be kept；
(3) in preparation process, all reagents are commercial product, do not need to be further processed；
(4) synthetic method is simple, and obtained material is easy to apply, and is conducive to promote and apply in industrialized production, may be used also
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.
Detailed description of the invention
Fig. 1 is to be carried on the nickel molybdenum base bimetallic carbide of nickel foam prepared by embodiment 1 to be carried in nickel foam
Digital photograph；
Fig. 2 is that 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 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 graph；
Fig. 4 is the X ray diffracting spectrum of nickel molybdenum base bimetallic carbide prepared by embodiment 1；
Fig. 5 is the X-ray absorption fine structure near side (ns) spectrum of nickel molybdenum base bimetallic carbide prepared by embodiment 1；
Fig. 6 is the space the R map of nickel molybdenum base bimetallic carbide prepared by embodiment 1；
Fig. 7 is the scanning electron microscopic picture that the nickel molybdenum base bimetallic carbide of nickel foam is carried on prepared by embodiment 1.
Specific embodiment
In the following, in conjunction with the accompanying drawings and embodiments, specific embodiments of the present invention are further described in detail, but do not answer
It is limited the scope of the invention with this.
" range " disclosed herein is in the form of lower and upper limit.It can be respectively one or more lower limits and one
Or multiple upper limits.Given range is defined by a selected lower limit and a upper limit.Selected lower and upper limit limit
The boundary of special range is determined.All ranges that can be defined in this way comprising and can combine, i.e., any lower limit
It can combine to form a range with any upper limit.For example, the range of 60-120 and 80-110 are listed for special parameter, reason
Solution is that the range of 60-110 and 80-120 is also to expect.In addition, if the minimum zone value 1 and 2 listed, and if list
Maximum magnitude 3,4 and 5, then below range can all expect: 1-2,1-4,1-5,2-3,2-4 and 2-5.
In the present invention, unless otherwise indicated, numberical range " a-b " indicates the breviary of any real combinings between a to b
It indicates, wherein a and b is real number.Such as numberical range " 0-5 " indicate herein all listed it is complete between " 0-5 "
Portion's real number, " 0-5 " are that the breviary of these combinations of values indicates.
In the present invention, if without particularly illustrating, all embodiments mentioned in this article and preferred implementation side
Formula can be combined with each other to form new technical solution.
In the present invention, if without particularly illustrating, all technical characteristics and preferred feature mentioned in this article can
New technical solution is formed to be combined with each other.
Preferred implementation method of the invention is specifically described below in conjunction with specific embodiment, but it is to be understood that ability
Field technique personnel can reasonably become these embodiments under the premise of the range limited without departing substantially from claims
Change, improve and be combined with each other, to obtain new specific implementation method, these are obtained by variation, improvement and intercombination
New specific 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)6Mo7O24·4H230mL is added in O and 0.1g glucose
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 is reacted 6 hours in 150 DEG C of baking oven, and cooled to room temperature later takes nickel foam
Out, and with deionized water it is cleaned, is placed in 60 DEG C of baking ovens and dries.Nickel foam after drying is packed into quartzy Noah's ark；It will be quartzy
Noah's ark is pushed into tube furnace central thermal zone position, and seals up ring flange；By hydrogen and argon gas after spinner flowmeter measures (hydrogen
Flow is 0.015L min-1, argon flow 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 by rate, and constant temperature handles 120min；Then, room temperature is naturally cooled to, takes out quartzy Noah's ark to get arriving
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 workstation, standard three electrode system, the nickel molybdenum base bimetallic carbon for being carried on nickel foam that will be obtained
Compound electrode is placed in the sulfuric acid of 0.5 mol/L and the potassium hydroxide aqueous solution of 1.0 mol/Ls, is carried out using conventional method
Liberation of hydrogen linear scan test.
Fig. 1 is the electronic photo of product, it can be seen that prepared nickel molybdenum base bimetallic carbide fairly evenly loads
In foam nickel surface.
Fig. 2 is the nickel molybdenum base bimetallic carbide and comparative experiments sample that nickel foam is carried on prepared by embodiment 1
Liberation of hydrogen linear scan curve as working electrode.Wherein: curve 1 is the nickel molybdenum to be carried on nickel foam prepared by embodiment 1
Bimetallic carbide is working electrode, and silver-silver chloride electrode is reference electrode, and graphite rod is to electrode, and hydrogen saturation 0.5 is rubbed
That/liter sulfuric acid and 1.0 mol/L potassium hydroxide solutions are electrolyte, and test temperature is 25 DEG C, scanning speed is 50 millivolts/
Linear scan curve under second test condition.Curve 2 is to be carried on nickel foam as working electrode using commercialization Pt/C in comparative experiments,
Silver-silver chloride electrode is reference electrode, and graphite rod is to electrode, and hydrogen is saturated 0.5 mol/L sulfuric acid and 1.0 mol/L hydrogen
Potassium oxide solution is electrolyte, and test temperature is 25 DEG C, and scanning speed is that the linear scan under 50 mv ss test conditions is bent
Line.Curve 3 is using blank nickel foam in comparative experiments as working electrode, and silver-silver chloride electrode is reference electrode, and graphite rod is pair
Electrode, hydrogen is saturated 0.5 mol/L sulfuric acid and 1.0 mol/L potassium hydroxide solutions are electrolyte, and test temperature is 25 DEG C,
Scanning speed is the linear scan curve under 50 mv ss 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 the nickel molybdenum base bimetallic carbide for being carried on 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 in 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, and the nickel molybdenum base bimetallic of nickel foam is carried on 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 can be seen that from Fig. 3 Dependence Results using 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 are respectively maintained at -70mV and -40mV or so without obvious decline.It proves using this
The prepared nickel molybdenum base bimetallic carbide for being carried on nickel foam of invention has preferable stability as electrode.
Fig. 4 is that ultrasound is got off the X ray diffracting spectrum of after drying powder from the nickel foam of preparation, is identified as
Mo6Ni6C.Scanning speed is 3 ° of min-1, scanning range is 36 °~79 ° of X ray diffracting spectrum.
Fig. 5 is that the X-ray absorption fine structure near side (ns) of product is composed.Wherein: curve 1 is standard sample molybdenum powder, curve in a figure
2 be the powder after drying that got off with ultrasound in nickel foam prepared by embodiment 1, and curve 3 is standard sample molybdenum trioxide；b
Curve 1 is standard sample nickel monoxide in figure, and curve 2 is to be got off with ultrasound in nickel foam prepared by embodiment 1 by drying
Powder afterwards, curve 3 are 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 that it differs larger with molybdenum trioxide and nickel monoxide on electronic structure in valence state, with molybdenum
Powder is more close with nickel powder, is lower valency, it was demonstrated that its intrinsic metallicity.
Fig. 6 is the space the R map 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 is to surpass in nickel foam prepared by embodiment 1
Sound gets off the powder after drying, and curve 2 is standard sample molybdenum powder.
By comparing curve in Fig. 6 it is found that Mo6Ni6The extension side Fourier transform results of molybdenum element are similar with molybdenum powder in C.
Two curves existAndNeighbouring obvious appearance, illustrates tungsten oxide Mo6Ni6The coordination information and molybdenum powder more class of C
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, and by observing sample topography, material is uniform in the covering of foam nickel surface, to receive
Rice grain forms rodlike cluster, and particle size is at 50 nanometers, and for shape to be irregular spherical, rodlike cluster scale is 1.0 microns.
Compared with existing electrocatalytic hydrogen evolution material preparation method, the invention has the following advantages that synthesis process is simple, it is former
Material selection is extensively, low in 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 is scattered in glucose and adds
Enter in 30mL deionized water, ultrasound is uniformly dispersed for 30 minutes, and obtained mixed solution is placed in the rigid set of polytetrafluoroethyllining lining
It is interior, it is put into 21 square centimeter of nickel foam, is reacted in 150 DEG C of baking oven 6 hours, it will bubble after cooled to room temperature
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 is packed into 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 0.085Lmin-1) be sufficiently mixed after enter tube furnace；With 5 DEG C of min-1
Rate tube furnace is warming up to 500 DEG C, constant temperature handles 120min；Then, room temperature is naturally cooled to, takes out quartzy Noah's ark, i.e.,
Obtain the nickel molybdenum base bimetallic carbide for being carried on 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 is scattered in glucose and adds
Enter in 30mL deionized water, ultrasound is uniformly dispersed for 30 minutes, and obtained mixed solution is placed in the rigid set of polytetrafluoroethyllining lining
It is interior, it is put into 21 square centimeter of nickel foam, is reacted in 150 DEG C of baking oven 6 hours, it will bubble after cooled to room temperature
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 is packed into 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 is 0.085L min-1) be sufficiently mixed after enter tube furnace；With 5 DEG C of min-1Rate tube furnace is warming up to 900 DEG C, constant temperature handles 120min；Then, room temperature is naturally cooled to, takes out quartzy Noah's ark, i.e.,
Obtain the nickel molybdenum base bimetallic carbide for being carried on nickel foam.Feature and performance are similar to Example 1.
The obtained material of the present invention is applied to 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 carry out at normal temperatures and pressures, wherein using silver-silver chloride electricity
Extremely reference electrode, graphite rod are to electrode, and hydrogen is saturated 0.5 mol/L sulfuric acid and 1.0 mol/L potassium hydroxide solutions
For electrolyte, test temperature is 25 DEG C.The foregoing is merely presently preferred embodiments of the present invention, all according to scope of the present invention patent
The equivalent changes and modifications done, are all covered by the present invention.
Claims (3)
1. a kind of preparation method for the nickel molybdenum base bimetallic carbide for being carried on nickel foam, which comprises the steps of:
(1) by 0.2~0.6g Nickelous nitrate hexahydrate, 0.3~0.7g tetra- is hydrated ammonium heptamolybdate and 0.05~0.25g grape sugar
It dissipates in 10~50mL deionized water, is 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, after cooled to room temperature, will be steeped with deionized water
Foam nickel is rinsed well, is placed in 60 DEG C of baking ovens and is dried for use；
(2) nickel foam is placed in the quartzy Noah's ark in tube furnace after the drying for taking 1~5 step (1) to obtain, with 0.05~0.3L
min-1It is passed through well-mixed carrier gas, reacts 60~180min, cooled 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 to get to the nickel molybdenum base bimetallic carbide Mo for being carried on nickel foam6Ni6C belongs to cubic system,
It is uniform in the covering of foam nickel surface, rodlike cluster is formed with nano particle, for particle size at 30~100 nanometers, shape is not advise
Then spherical, rodlike cluster scale is 0.5~1.5 micron.
2. the application of the nickel molybdenum base bimetallic carbide described in claim 1 for being carried on nickel foam, which is characterized in that described negative
The nickel molybdenum base bimetallic carbide of nickel foam is loaded in for the hydrogen manufacturing of electrocatalytic decomposition water.
3. application according to claim 2, which is characterized in that application method 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, using silver-silver chloride electrode as reference 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 more than hour can be kept；In alkaline electrolyte solution, when overpotential is -34mV
When, current density can reach 8~12mA cm-2, and steady-working state 300 more than hour can be kept.
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| CN112371119B (en) * | 2020-11-13 | 2023-07-07 | 中南大学深圳研究院 | Preparation method and application of multi-metal pairing alkaline catalyst |
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| CN112877728B (en) * | 2020-12-10 | 2022-08-09 | 上海航天智慧能源技术有限公司 | Platinum-carbon-layer-containing loaded foam nickel electrolytic water electrode and preparation method thereof |
| CN112941558B (en) * | 2020-12-30 | 2023-08-22 | 河南科技大学 | Preparation method of composite material catalytic electrode |
| CN113249735A (en) * | 2021-04-19 | 2021-08-13 | 北京化工大学 | Preparation method of efficient molybdenum carbide hydrogen evolution catalyst |
| CN113355687B (en) * | 2021-04-20 | 2022-05-24 | 广东石油化工学院 | Tin-based bimetallic carbide @ carbon nanochain core-shell structure and preparation method and application thereof |
| CN113846343A (en) * | 2021-07-17 | 2021-12-28 | 北京工业大学 | Preparation method of nickel-molybdenum carbide electrocatalyst |
| CN113584520B (en) * | 2021-07-26 | 2022-08-12 | 中国科学院广州能源研究所 | Super-hydrophilic molybdenum-doped tungsten carbide nano array material and preparation method thereof |
| CN114381757B (en) * | 2022-01-30 | 2023-08-25 | 中国华能集团清洁能源技术研究院有限公司 | Carbon-coated nickel-molybdenum-vanadium hydrogen evolution electrode and preparation method and application thereof |
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