CN106694006A - Preparation of highly dispersed molybdenum carbide/carbon composite electro-catalyst by adopting oxidation, reduction and fixation method - Google Patents
Preparation of highly dispersed molybdenum carbide/carbon composite electro-catalyst by adopting oxidation, reduction and fixation method Download PDFInfo
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- CN106694006A CN106694006A CN201611136653.8A CN201611136653A CN106694006A CN 106694006 A CN106694006 A CN 106694006A CN 201611136653 A CN201611136653 A CN 201611136653A CN 106694006 A CN106694006 A CN 106694006A
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Abstract
The invention relates to a preparation method of a highly dispersed molybdenum carbide/carbon composite electro-catalyst by adopting an oxidation, reduction and fixation method. The preparation method comprises the following steps that 1, reducing organic matter and ammonium heptamolybdate are dissolved in water to prepare a mixed solution, wherein the mass ratio of the reducing organic matter to the ammonium heptamolybdate is 1: (0.1-2); 2, the mixed solution is subjected to hydrothermal treatment at the temperature of 120-200 DEG C for 4-24 hours, solid is separated out, and washing and drying are performed; 3, the dried solid is calcined in a protective atmosphere at the temperature of 600-1000 DEG C for 2-10 hours to obtain the highly dispersed molybdenum carbide/carbon composite electro-catalyst. The used raw materials are safe, non-toxic, simple to obtain and convenient to prepare and can be synthesized into molybdenum carbide nanomaterials in a large-scale mode.
Description
Technical field
High dispersive molybdenum carbide/carbon composite electrocatalyst is prepared the present invention relates to a kind of redox fixing means, belongs to electricity
Catalysis technical field.
Background technology
Water electrolysis hydrogen production is a kind of preferable hydrogen manufacturing mode of high-efficiency environment friendly.Current optimal platinum based catalyst due to
Its price is high, resource-constrained, limits its application industrially.Therefore find and find efficient, cheap base metal
Elctro-catalyst, is the key of water electrolysis hydrogen production reaction.At present, some early stage transition metal, such as Fe, Co, Ni, Mo, W etc., they
Metal alloy and carbide, nitride, sulfide, phosphide of composition etc., are widely used for research as electrolysis water system
The catalyst of hydrogen.Wherein, β-Mo2C due to its good electrical conductance, preferable hydrogen adsorption capacity, chemical stability and its is only
The electronic structure of special class noble metal, is one of optimal base metal elctro-catalyst for being widely studied in recent years.It is reported that
Commercialized β-Mo2C just has the catalytic performance of electro-catalysis hydrogen manufacturing, but its catalytic performance is compared in commercialized platinum carbon, is still had
Very big gap.
The catalytic performance of carbonization Mo can expose more active sites by preparing molybdenum carbide nanostructured, or
It is supported on the conductive carriers such as Graphene, carbon pipe to improve.At present, because carbonization Mo is under preparation process high temperature
Have inevitable aggregation procedure or a undue growth, and molybdenum carbide surface partial oxidation, the molybdenum carbide for preparing high dispersive receives
Rice structure is still a challenge.The method for being used for preparing molybdenum carbide nanostructured at present mainly has, and one is by the confinement of MOF
Effect prepares molybdenum carbide nanostructured, and two be by MoOx-NH2The method of coordination, prepares the presoma of nanometer high dispersive first
Material, then high temperature cabonization obtain molybdenum carbide nanostructured.But usual these methods prepare complicated, condition harshness.
The content of the invention
Regarding to the issue above, it is an object of the invention to provide a kind of flow is simple, economical rationality, environment-friendly, Yi great
The synthetic method of the molybdenum carbide nanostructured of large-scale production, and the molybdenum carbide nano material for preparing has good water electrolysis hydrogen production
Performance.
Herein, on the one hand, the present invention is provided one kind and is combined using redox fixing means preparation high dispersive molybdenum carbide/carbon
The method of elctro-catalyst, comprises the following steps：
1) mixed solution is configured to by organic matter and ammonium heptamolybdate with reproducibility are soluble in water, wherein the organic matter with reproducibility
It is 1 with the mass ratio of ammonium heptamolybdate：(0.1~2)；
2) by the mixed solution, hydro-thermal process isolates solid after 4~24 hours at 120~200 DEG C, and washs, dries；
3) by dried solid under protective atmosphere in 600~1000 DEG C calcine 2~10 hours, obtain high dispersive molybdenum carbide/
Carbon composite electrocatalyst.
The present invention gives up traditional MoOx-NH2The precursor synthesis method of coordination, disperses to fix using a kind of redox
The method of presoma prepares the molybdenum carbide/carbon composite electrocatalyst of high dispersive, specifically, with reductive organic matter as carbon
Source, ammonium heptamolybdate ((NH4)6Mo7O24.4H2O it is) molybdenum source, it is anti-using hydro-thermal dexterously using the redox between them
Should, obtain MoO2/ C compounds, then high temperature cabonization obtains the molybdenum carbide/carbon composite electro catalytic of high dispersive under protective atmosphere
Agent.The raw materials used safety non-toxic of the present invention, supplied materials is simple, and it is convenient to prepare, and can on a large scale synthesize molybdenum carbide nano material.
It is preferred that it is ethylene glycol, glycerine, citric acid, glucose, sucrose and shallow lake that the organic matter with reproducibility is selected from
At least one in powder.
It is preferred that in the mixed solution, the concentration of ammonium heptamolybdate is 0.002~0.1g/mL.
It is preferred that step 3) in, programming rate is 2~10 DEG C/min.
It is preferred that step 3) in, the protective atmosphere is the mixed atmosphere of inert atmosphere or hydrogen and inert gas.
On the other hand, the present invention provides the high dispersive molybdenum carbide/carbon composite electrocatalyst prepared by the above method, its bag
Include：Carbon base body and the molybdenum carbide nano particle being fixed and dispersed within the carbon base body.
Molybdenum carbide of the invention/carbon composite electrocatalyst is presented the architectural feature of high degree of dispersion, and molybdenum carbide is nano junction
Structure, therefore with excellent electro-catalysis hydrogen manufacturing performance.For example, by 0.5M H2SO4LSV curves are surveyed in solution to assess carbonization
During the water electrolysis hydrogen production catalytic performance of molybdenum/carbon composite electrocatalyst, it is in 20mA/cm2Overpotential under current density is 193-
267mV (with respect to reversible hydrogen electrode), Tafel slope is 83-108mV/dec, and continuously operation 10h still keeps good steady
It is qualitative.
In the present invention, the molybdenum carbide is η-MoC and β-Mo2Both C mixed phases.
In the present invention, the size of the molybdenum carbide nano particle can be adjusted by the addition of ammonium heptamolybdate.
In the present invention, the mean size of the molybdenum carbide nano particle can be 5~40nm.
Another further aspect, the present invention provides above-mentioned high dispersive molybdenum carbide/carbon composite electrocatalyst answering in electro-catalysis hydrogen manufacturing
With.
The present invention is advantageous in that：The present invention proposes a kind of simple flow, economical rationality, nanostructure size can
Tune, the synthetic method of the molybdenum carbide nanostructured of environment-friendly, easy large-scale production.The present invention is using reductive organic matter and height
The direct redox reaction of valency molybdenum source, molybdenum carbide persursor material is obtained using redox method, then pyrocarbon again
Change obtains the molybdenum carbide/carbon composite catalytic agent of high dispersive.Synthetic method supplied materials of the invention is simple, equipment requirement is low, it is simple to prepare
List, and the material nano size adjustable for synthesizing, stable performance can be prepared on a large scale, can be used for the catalytic reaction of water electrolysis hydrogen production,
But not limited to this catalytic reaction, is expected to produce good social and economic benefit.
Brief description of the drawings
Fig. 1 is the XRD after prepared molybdenum carbide/carbon composite catalytic agent before calcination；
Fig. 2 a-2c are the BSE-SEM figures before sample calcining after hydro-thermal process；
Fig. 3 a-3c are the BSE-SEM figures of prepared molybdenum carbide/carbon composite catalytic agent；
Fig. 4 is that the water electrolysis hydrogen production catalytic performance of prepared molybdenum carbide/carbon composite catalytic agent characterizes curve；
Fig. 5 is that the stability of the water electrolysis hydrogen production of prepared molybdenum carbide/carbon composite catalytic agent is characterized.
Specific embodiment
The present invention is further illustrated below in conjunction with accompanying drawing and following implementation methods, it should be appreciated that accompanying drawing and following implementation methods
The present invention is merely to illustrate, is not intended to limit the present invention.
The present invention prepares high dispersive molybdenum carbide/carbon composite electrocatalyst, specific bag using a kind of redox fixing means
Include following steps：1) organic matter and ammonium heptamolybdate with reproducibility of certain mass are weighed；2) certain water is added to be allowed to dissolve；3) will
Mixed liquor is fitted into water heating kettle, and hydro-thermal obtains black product at a certain temperature；4) black product is washed, separated, is dried；5)
Desciccate is calcined the molybdenum carbide/carbon composite electrocatalyst that can obtain high dispersive under protective atmosphere.Hereinafter, as showing
Example, illustrates the method for the present invention.
By the organic matter with reproducibility and ammonium heptamolybdate ((NH4)6Mo7O24.4H2O it is) soluble in water, form mixed solution.Band
The organic matter of reproducibility may be selected from polyalcohol, citric acid, glucide etc., for example, may be selected from ethylene glycol, glycerine, citric acid,
And at least one in the glucide such as glucose, sucrose, starch.The mass ratio of organic matter and ammonium heptamolybdate with reproducibility
Can be 1：(0.1~2).In mixed solution, the concentration of ammonium heptamolybdate can be 0.002~0.1g/mL.In one example, band is gone back
The quality of the organic matter of originality is 1-5g, and the quality of ammonium heptamolybdate is 0.1-5g, and the volume of water is 50mL.To promote to dissolve, can
Stirring, ultrasound etc..
Mixed solution is transferred in water heating kettle, hydro-thermal process 4-24 hours at 120-200 DEG C, black product is obtained.
By after hydro-thermal process, molybdenum source is by redox reaction with MoO2Form be fixed and dispersed within carbon material, obtain MoO2/ C's
Compound.MoO can be adjusted by adding the amount of molybdenum source2Granular size so as to adjust the particle of molybdenum carbide for finally giving big
It is small.
By black product centrifuge washing, and dry, such as dried at a temperature of 60 DEG C.
Dry black product is placed in atmosphere furnace and calcines.Calcination atmosphere can be protective atmosphere, such as N2, the inertia such as Ar, He
Atmosphere, or the H with reducing property2/ Ar gaseous mixtures.Calcining heat is 600~1000 DEG C, preferably 750~850 DEG C.
Programming rate can be 2~10 DEG C/min.Soaking time can be 2-10h.Through calcining, MoO2MoO in/C2It is molybdenum carbide to be carbonized.
After temperature lowers, you can obtain the molybdenum carbide/carbon composite catalytic agent of high dispersive.
The molybdenum carbide of gained/carbon composite catalytic agent includes carbon base body and the molybdenum carbide being fixed and dispersed within the carbon base body
Nano particle.Molybdenum carbide nano particle is in high dispersion state.Molybdenum carbide is η-MoC and β-Mo2Both C mixed phases, are designated as MoCx。
Combinations of the MoC to hydrogen can relative Mo2C is weak, and this is conducive to the desorption of hydrogen in electrolysis water.The size of molybdenum carbide nano particle
Can be adjusted by adding the amount of molybdenum source (ammonium heptamolybdate), for example its mean particle size is adjustable between 5~40nm.With
The amount for addition molybdenum source (ammonium heptamolybdate) increases, the size increase of molybdenum carbide particles in the molybdenum carbide for obtaining/carbon composite catalytic agent.
And the size and/or content of molybdenum carbide nano particle can further influence the overpotential of molybdenum carbide/carbon composite catalytic agent
(water electrolysis hydrogen production catalytic performance).
It is of the invention to be distinguished by：The present invention gives up traditional MoOx-NH2The precursor synthesis method of coordination, uses
A kind of method of the fixed presoma of redox dispersion prepares the molybdenum carbide/carbon composite electrocatalyst of high dispersive, raw materials used
Safety non-toxic, the molybdenum carbide/carbon composite catalytic agent sized particles size adjustable, the catalytic with excellent water electrolysis hydrogen production
Energy.
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright the above is made belong to protection scope of the present invention.Following examples are specific
Technological parameter etc. is also only that an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1
Selection citric acid is reproducibility carbon source, weighs citric acid 2.5g and ammonium heptamolybdate ((NH4)6Mo7O24.4H2O) 0.5g is in burning
In cup, plus 50mL water ultrasonic dissolutions, it is then transferred into water heating kettle, the hydro-thermal 8h at 180 DEG C, after cooling, by black product
Washing centrifugation, dries.By dried product in H2800 DEG C are calcined to under/Ar atmosphere, programming rate is 5 DEG C/min, insulation
5h, you can obtain molybdenum carbide/carbon composite catalytic agent, be designated as MoCx-1。
The electro-chemical test of obtained high dispersive molybdenum carbide/carbon composite catalytic agent water electrolysis hydrogen production is carried out according to the following steps：
First, weighing the above-mentioned catalyst of 4mg, to be dispersed in the mixing comprising 1mL absolute ethyl alcohols and 40uL Nafion solutions (5%) molten
In liquid, ultrasound obtains dispersed suspension, then takes the above-mentioned hanging drops of 30uL to the ripple carbon electrode of a diameter of 6mm,
Working electrode is can obtain after natural drying；Then the test of electrochemistry hydrogen manufacturing performance is in electrochemical workstation (CHI760E, Shanghai
Occasion China) carry out, using three-electrode system, with 0.5M H2SO4Solution is electrolyte, and graphite rod is that, to electrode, 3M KCl solution is filled out
The Ag/AgCl electrodes for filling are reference electrode, and the speed of sweeping of linear sweep voltammetry curve is 10mV/s, and experimental data does not carry out IR schools
Just, electrode potential is relative to reversible hydrogen electrode (RHE), and conversion method is as follows：ERHE=EAg/AgCl+0.059*pH+0.209。
Embodiment 2
Preparation process and step in embodiment 2 is essentially identical with above-described embodiment 1, unlike：The molybdic acid of molybdenum source seven for weighing
Ammonium ((NH4)6Mo7O24.4H2O) quality is 2.5g, and obtained catalyst is designated as MoCx-2.The water electrolysis hydrogen production catalytic of catalyst
Can characterize with embodiment 1.
Embodiment 3
Preparation process and step in embodiment 3 is essentially identical with above-described embodiment 1, unlike：The molybdic acid of molybdenum source seven for weighing
Ammonium ((NH4)6Mo7O24.4H2O) quality is 4g, and obtained catalyst is designated as MoCx-3.The water electrolysis hydrogen production catalytic performance of catalyst
Characterize with embodiment 1.
Fig. 1 a are the XRD of sample after hydro-thermal process is dried, and Fig. 1 b are the XRD after protective atmosphere calcining.From Fig. 1 a
As can be seen that the sample after hydro-thermal process is MoO2The compound of/C, shows by after hydro-thermal process, molybdenum source is gone back by oxidation
Original reaction is with MoO2Form be fixed and dispersed within carbon material.It is existing from Fig. 1 b as can be seen that after protective atmosphere is calcined
β-Mo2The phase of C, the phase for having η-MoC again is both mixed phases, is designated as MoCx。
Fig. 2 a-2c are the BSE-SEM figures before sample calcining after hydro-thermal process.Fig. 2 a, b, c correspond to MoC respectivelyx- 1, MoCx-
2, MoCxBSE-SEM figures before -3 calcinings.With reference to XRD, bright part is MoO in Fig. 2 a-2c2Nano particle, dark is carrier
Carbon.The method fixed by this redox is can be seen that from Fig. 2 a-2c, molybdenum species are uniformly fixed on carbon carrier
Go up, and molybdenum species granular size can be adjusted by adding the amount of molybdenum source.
Fig. 3 a-3c are the BSE-SEM figures of prepared molybdenum carbide/carbon composite catalytic agent.Fig. 3 a, b, c correspond to MoC respectivelyx-
1, MoCx- 2, MoCx- 3 BSE-SEM figures.Expression MoC bright in Fig. 3 a-3cxNano particle, dark is carrier carbon.From Fig. 3 a-
As can be seen that MoC in 3cx- 1 mean particle size is 5-10nm, MoCx- 2 mean particle size is 10nm, MoCx- 3
Mean particle size is 30-40nm, this explanation MoCxThe size of particle can be adjusted by adding the amount of molybdenum source.
Fig. 4 is that the water electrolysis hydrogen production catalytic performance of prepared molybdenum carbide/carbon composite catalytic agent characterizes curve, wherein Fig. 4 a
It is linear sweep voltammetry curve, Fig. 4 b are Tafel curve.As can be seen that when current density is 20mA/cm from Fig. 4 a2,
MoCx-1、MoCx-2、MoCxOverpotential required for -3 is respectively 252mV, 193mV, 267mV, and this shows MoCxElectrolysis water system
Hydrogen catalysis performance depends on MoCxParticle size, with MoCxContent it is relevant.As can be seen that MoC from Fig. 4 bx-1、MoCx-
2、MoCx- 3 Tafel slope is respectively 96mV/dec, 83mV/dec, 108mV/dec, shows their rate-limiting step
All it is Volmer-Heyrovsky steps.
Fig. 5 is the MoC for preparingxThe i-t stability tests of -2 catalyst, after 10h is run, current density is stilled remain in
5mA/cm2Left and right, shows its good stability.
Claims (10)
1. a kind of method that use redox fixing means prepares high dispersive molybdenum carbide/carbon composite electrocatalyst, its feature exists
In comprising the following steps：
1）Mixed solution is configured to by organic matter and ammonium heptamolybdate with reproducibility are soluble in water, wherein the organic matter with reproducibility
It is 1 with the mass ratio of ammonium heptamolybdate：（0.1~2）；
2）By the mixed solution, hydro-thermal process isolates solid after 4~24 hours at 120~200 DEG C, and washs, dries；
3）By dried solid under protective atmosphere in 600~1000 DEG C calcine 2~10 hours, obtain high dispersive molybdenum carbide/
Carbon composite electrocatalyst.
2. method according to claim 1, it is characterised in that it is ethylene glycol, third that the organic matter with reproducibility is selected from
At least one in triol, citric acid, glucose, sugarcane sugar and starch.
3. method according to claim 1 and 2, it is characterised in that in the mixed solution, the concentration of ammonium heptamolybdate is
0.002~0.1g/mL.
4. according to the method in any one of claims 1 to 3, it is characterised in that step 3）In, programming rate is 2~10
DEG C/min.
5. method according to any one of claim 1 to 4, it is characterised in that step 3）In, the protective atmosphere is lazy
The mixed atmosphere of property atmosphere or hydrogen and inert gas.
6. high dispersive molybdenum carbide/carbon composite electrocatalyst that prepared by a kind of method as any one of claim 1 to 5,
It is characterised in that it includes：Carbon base body and the molybdenum carbide nano particle being fixed and dispersed within the carbon base body.
7. high dispersive molybdenum carbide/carbon composite electrocatalyst according to claim 6, it is characterised in that the molybdenum carbide is
η-MoC and β-Mo2Both C mixed phases.
8. the high dispersive molybdenum carbide/carbon composite electrocatalyst according to claim 6 or 7, it is characterised in that the molybdenum carbide
The size of nano particle is adjusted by the addition of ammonium heptamolybdate.
9. the high dispersive molybdenum carbide/carbon composite electrocatalyst according to any one of claim 6 to 8, it is characterised in that institute
The mean size for stating molybdenum carbide nano particle is 5~40nm.
10. the high dispersive molybdenum carbide/carbon composite electrocatalyst any one of a kind of claim 6 to 9 is in electro-catalysis hydrogen manufacturing
In application.
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