CN106876728A - Monatomic graphene-based catalyst of load of high density transition metal and preparation method thereof - Google Patents
Monatomic graphene-based catalyst of load of high density transition metal and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides a kind of preparation method of the monatomic graphene-based catalyst of load of high density transition metal, comprise the following steps：Nitrogenous precursor, carbon source and soluble transition metal salt are dissolved in water, is then dried by evaporation, ground, calcining and obtain the high density transition metal graphene-based catalyst of monatomic load.Merely with soluble metallic salt, using glucose etc. as carbon source, dicyanodiamine has only just successfully prepared the effective catalyst with high activity site density monatomic loading high using one-step calcination method to the present invention as nitrogen doping source.
Description
Technical field
It is graphene-based the present invention relates to catalyst technical field, more particularly to a kind of monatomic load of high density transition metal
Catalyst and preparation method thereof.
Background technology
Research catalytic action avtive spot has vital meaning, substantial amounts of experiment to exploitation efficient catalyst
Fact proved that the atom that metal and its alloy catalyst only have particle surface plays catalytic action so that the utilization rate of atom drops significantly
It is low.Rise and prosperity with nanometer technology, it has been found that reduce the size of catalyst activity partial particulate, improve avtive spot
Quantity and dispersiveness, are conducive to improving the utilization rate and catalytic capability of catalyst.
With the proposition of monatomic concept in recent years, the monatomic site catalysts of synthesis show high activity, high
The feature such as selectivity and high stability, is that current your gold solved while realizing the utilization to greatest extent of catalytic site atom
Metal catalyst is expensive, the effective way of shortage of resources.
The monatomic catalyst of most of synthesis has the problems such as load capacity is too low, and preparation method is complicated at present, seriously
Constrain its large-scale commercial applications.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of monatomic load stone of high density transition metal
Mertenyl catalyst and preparation method thereof, the catalyst of preparation has load capacity and catalysis activity higher.
It is to solve above technical problem, graphene-based is urged the invention provides a kind of monatomic load of high density transition metal
The preparation method of agent, comprises the following steps：
Nitrogenous precursor, carbon source and soluble transition metal salt are dissolved in water, is then dried by evaporation, grinds, forged
Burning obtains the monatomic graphene-based catalyst of load of high density transition metal.
Methods described is specially：
Nitrogenous precursor and carbon source are dissolved in water first.
The nitrogenous precursor is dicyanodiamine, and it has stronger complexing power easily to form decentralization more with metal ion
Monatomic catalyst high, and other raw materials such as urea easily form some metal carbides and nitride after high-temperature process
Nano particle loads the situation of Graphene.
The carbon source is organic carbohydrate, preferably glucose or sucrose.
The mass ratio of the carbon source and nitrogenous precursor is preferably greater than 1:20.So that Fe is monatomic as an example, it is preferred that Liang Zhezhi
Amount ratio is 1:Performance of oxygen-reducing catalyst obtained by when 20 is best.Found in optimization process, the ratio shared by dicyanodiamine is got over
Greatly, the specific surface area of catalyst of final gained is bigger, but hydrogen reduction performance does not have further raising, and reason is ratio high
There is surface area excessively fluffy structure to prevent the diffusion process of oxygen, so as to reduce catalytic performance.
The present invention is to the consumption of water and is not particularly limited, and can dissolve nitrogenous precursor and carbon source.
When nitrogenous precursor is dicyanodiamine, its solubility in water about 2.26% (13 DEG C) can be according to actually adding
The amount of dosage regulation addition water is until dicyanodiamine all dissolves.
The present invention is to the transition metal atoms in the soluble transition metal salt and is not particularly limited, and can be this area
Transition metal atoms known to technical staff, in some embodiments of the invention, the transition metal atoms be Fe,
One or more in Co, Ni, Cu, Pt, Pd and Ru.
The present invention is to its anion and is not particularly limited, and water can be dissolved in, present invention preferably employs hydrochloride, sulfuric acid
The slaines such as salt, nitrate.
Then above-mentioned soluble transition metal saline solution is mixed with the aqueous solution of nitrogenous precursor and carbon source, is contained
The mixed solution of presoma.
When the nitrogenous precursor is dicyanodiamine, and carbon source is glucose, it is with 5g dicyanodiamines and 0.25g glucose
Example, the addition of soluble metallic salt is preferably 0~0.0375mmol, described to add in some embodiments of the invention
Dosage is 0.025mmol.Found in optimization process, if metal addition is more than 0.0375mmol, some carbonizations can be generated
Thing and nitride nano particle, this reunion for having reached maximum and having occurred mainly due to the loading of metallic atom.It is based on
Zooming in or out for this equal proportion can also obtain similar conclusion.
Then drying is evaporated to the above-mentioned mixed solution containing presoma, obtains recrystallizing solid.
The present invention is to the method for the evaporation drying and is not particularly limited, and can be evaporation well known to those skilled in the art
, in some embodiments of the invention, can be put into mixed solution on warm table and be evaporated by dry conventional method.
The temperature of the evaporation drying is preferably 80 DEG C of ＜, more preferably 60-80 DEG C, in case temperature is too high, dicyanodiamine
Decompose, or glucose is carbonized.
Then by above-mentioned recrystallization solid abrasive into powder.
Finally above-mentioned powder is calcined under an inert atmosphere, you can obtain the monatomic load Graphene of high density transition metal
Base catalyst.
In the monatomic graphene-based catalyst of load of high density transition metal of preparation, C atoms, N atoms and metal raw
The mol ratio of son is 100：(9~20)：(0~2.2).
In some embodiments of the invention, during the powder is put into the quartz boat of suitable size or corundum boat and
Add a cover top；Then sample is placed in tube furnace, is calcined under an inert atmosphere.
The inert atmosphere can be the conventional inert atmosphere in this area, in some embodiments of the invention, institute
Inert atmosphere is stated for nitrogen or argon gas.
The temperature of the calcining is preferably 750 DEG C of ＞, more preferably 800-1000 DEG C, produced in chilling process to ensure
Carbonitride all decompose；In some embodiments of the invention, the calcining heat is 900 DEG C；The calcining when
Between be preferably 1~3h.
Found in optimization process, when temperature is more than 750 DEG C, the carbonitride produced by dicyanodiamine is all decomposed, part
Nitrogen-atoms is entered into the glycogenetic carbon lattice of grape, and serves the effect of fixed metallic atom.And with the monatomic preparations of Fe
Catalyst material as a example by, when calcining heat is 900 DEG C, the performance of oxygen-reducing catalyst that is obtained preferably, this be mainly because
It is that playing promotion to catalyst performance lifting makees as the electronic conductivity matter at the graphene-based bottom of raising of temperature is gradually stepped up
With；And further rising high-temperature can reduce nitrogen content, part metals atom can also reunite, so that hydrogen reduction performance drops
It is low.
Above-mentioned preparation method process is simple, and source chemicals are common to be easy to get and cost is relatively low, simple and easy to apply and stability preferably,
It is adapted to large-scale production.The Fe-N-C structures for especially being built centered on monatomic by Fe show outstanding hydrogen reduction
Can, it is expected to realize large-scale application in fuel cell field substitution Pt noble metal catalysts.
The monatomic load of high density transition metal prepared present invention also offers a kind of above-mentioned preparation method is graphene-based
Catalyst, the catalyst includes carbon, nitrogen and transition metal, wherein the atomic ratio of transition metal and carbon for 0~
2.2at.%, nitrogen is 9~20at.% with the atomic ratio of carbon.The catalyst is graphene film Rotating fields, with high-ratio surface
Product, and can be regulated and controled by changing the ratio of dicyanodiamine.
The catalyst have active, dispersed and load capacity higher, larger specific surface area, it has similar oxidation
The Wrinkled flake structure of Graphene, nitrogen-atoms is played when adulterating among the lattice of class graphitic carbon material to metallic atom
Grappling effect, is made single metal atom be uniformly anchored on by the coordination with nitrogen many active sites is formed among graphene sheet layer
The catalyst of point.Test result also show the thin layer that catalyst structure is dispersed in fold for transition metal in monoatomic form
On graphene sheet layer.
The monatomic graphene-based catalyst of load of above-specified high density transition metal that the present invention is provided can be used for various catalysis
Reaction, so that Fe provided in an embodiment of the present invention is monatomic as an example, it can be used for PEM as cathodic oxygen reduction catalyst
Fuel cell or metal-air battery field.
Same the catalyst prepared to the above method carries out hydrogen reduction performance test so that Fe is monatomic as an example, contrasts business
The platinum carbon catalyst of industry, catalyst oxygen reduction catalysis activity prepared by the application is in alkaline (0.1mol/L KOH) condition and acid
Property (0.1mol/L HClO4) under the conditions of, business platinum carbon catalyst of the performance with 20% is suitable.Its take-off potential is respectively
998mV, 876mV, half wave potential are respectively 845mV, 658mV.
Preparation method of the present invention, it is only necessary to some less expensive raw materials being easy to get, such as glucose, dicyanodiamine,
Metal inorganic salt etc., in processing mode only with water as solvent dissolving mix precursor material, only make use of one-step calcination method just into
Work(has prepared the effective catalyst with high activity site density monatomic loading high.
Calcine the inert atmosphere for using relatively safety and also easily realize that the small part ammonia produced in sintering process (comes from
In the decomposition of dicyanodiamine) it is easily processed, it is that a kind of can on a large scale prepare the safe and simple of the monatomic catalyst of transition metal
Method.
By taking the monatomic catalyst of Fe prepared by the application as an example, carry out hydrogen reduction performance test and show, in alkaline electrolyte
The size of the catalyst of middle Fe-N structures its take-off potential, half wave potential and carrying current value will should better than commercialization at present
Platinum carbon catalyst；In addition, hydrogen reduction performance is also close to business platinum carbon in acidic electrolysis bath.And the monatomic catalysis of Fe
The problem that agent poisons in the absence of carbon monoxide or methyl alcohol, while also possessing good cyclical stability.
Brief description of the drawings
Fig. 1 is the X ray diffracting spectrum (XRD) of embodiment 1, comparative example 1 and comparative example 2；
Fig. 2 is that embodiment 1 prepares transmission electron microscope (TEM) shape appearance figure (a) and secondary angstrom level of sample to differentiate details in a play not acted out on stage, but told through dialogues scanning saturating
Penetrate electron micrograph (HAADF-STEM) (b)；
Fig. 3 is the TEM figures that comparative example 1 prepares sample；
Fig. 4 is the TEM figures that comparative example 2 prepares sample；
Fig. 5 be embodiment 2 in 0.1mol/L KOH solutions, under oxygen saturated conditions, rotating speed is 1600rpm, sweeps speed and is
Linear sweep voltammetry curve during 5mV/s；
Fig. 6 is embodiment 3 in 0.1mol/L HClO4In solution, under oxygen saturated conditions, rotating speed is 1600rpm, sweeps speed
Linear sweep voltammetry curve during for 5mV/s；
Fig. 7 be embodiment 4, embodiment 5 in 0.1mol/L KOH solutions, under oxygen saturated conditions, rotating speed is
1600rpm, linear sweep voltammetry curve when sweeping speed for 5mV/s；
Fig. 8 be embodiment 6 prepare sample scanning transmission electron microscope (STEM) shape appearance figure (a) and secondary angstrom level differentiate details in a play not acted out on stage, but told through dialogues sweep
Retouch transmission electron microscopy figure (HAADF-STEM) (b).
Specific embodiment
It is monatomic to the high density transition metal that the present invention is provided with reference to embodiment in order to further illustrate the present invention
Graphene-based catalyst and preparation method thereof is loaded to be described in detail.
Embodiment 1
A. the glucose of 0.25g and the dicyanodiamine of 5g are weighed and the two is dissolved in (attention in the deionized water of 200mL
Because solubility of the dicyanodiamine in water is relatively low, it is also required to increase the amount of water simultaneously when its quality is increased until reagent dissolves
Completely)；
B. measure the molar concentration that 2mL configures with liquid-transfering gun and be the liquor ferri trichloridi of 0.0125mol/L, and be added drop-wise to
In the glucose and dicyanodiamine solution that have dissolved；
C. the good solution containing presoma of above-mentioned configuration is put on 80 DEG C of warm tables and is evaporated, then taken out and ground with mortar
Wear into uniform powder, and put it into the quartz boat or corundum boat of suitable size and top is added a cover；
D. then Noah's ark is integrally placed in tube furnace, (nitrogen or argon gas) 900 DEG C of calcinings 2 are small under an inert atmosphere
When, and Temperature fall.
The catalyst for preparing is detected using XRD, as a result sees Fig. 1, gained sample is can be seen that from the XRD results of Fig. 1
Product only have the diffraction maximum of carbon, not because ferric trichloride be added in high-temperature calcination in the case of form the nanometer of crystallization
Grain, illustrates that it is mainly what is existed in unformed form.Further show that (result is shown in figure by HAADF-STEM characterization methods
2), iron is uniformly supported on graphene-based bottom in the scattered form of atom level.
Comparative example 1
A. the glucose of 0.25g and the urea of 5g are weighed and the two is dissolved in the deionized water of 200mL；
B. measure the molar concentration that 2mL configures with liquid-transfering gun and be the liquor ferri trichloridi of 0.0125mol/L, and be added dropwise to
To in the glucose and urea liquid for having dissolved；
C. the solution containing presoma that will have been configured is put on 80 DEG C of warm tables and is evaporated, then take out with mortar grinder into
Uniform powder, and put it into the quartz boat or corundum boat of suitable size and top is added a cover；
D. then Noah's ark is integrally placed in tube furnace, (nitrogen or argon gas) 900 DEG C of calcinings 2 are small under an inert atmosphere
When, and Temperature fall.
The catalyst for preparing is detected using XRD, as a result sees Fig. 1, gained sample is can be seen that from the XRD results of Fig. 1
Product also belong to Fe except the diffraction maximum of carbon3The peak of C compounds, illustrates that added source of iron is sent out in the case of high-temperature calcination
Reunion is given birth to.Further show that (result is shown in Fig. 3, wherein figure a is low power number transmission electron microscope picture, figure b is by TEM characterization methods
Nano particle high-resolution crystal lattice pattern), really with the presence of ten a few to tens of nanometers not wait particle and be supported on graphene-based bottom.
Comparative example 2
A. the glucose of 0.25g and the dicyanodiamine of 5g are weighed and the two is dissolved in the deionized water of 200mL；
B. the solution containing presoma that will have been configured is put on 80 DEG C of warm tables and is evaporated, then take out with mortar grinder into
Uniform powder, and put it into the quartz boat or corundum boat of suitable size and top is added a cover；
C. then Noah's ark is integrally placed in tube furnace, (nitrogen or argon gas) 900 DEG C of calcinings 2 are small under an inert atmosphere
When, and Temperature fall.
The catalyst for preparing is detected using XRD, as a result sees Fig. 1, gained sample is can be seen that from the XRD results of Fig. 1
There is the diffraction maximum of carbon in product, the peak of carbonitride is not belonged to, illustrate by the nitridation produced by high-temperature calcination (900 DEG C) low temperature
Carbon has all been decomposed and had among the lattice that small part nitrogen enters carbon.Further by TEM characterization methods (result is shown in Fig. 4) table
Bright, it is presented few graphene sheet layer pattern of the layer with fold, and this is mainly due to the carbonitride formed in chilling process
Typical two-dimensional layer material,, equivalent to a template in building-up process, the carbonization to glucose serves the work of confinement for it
With so as to its sintering will not be made blocking.
Embodiment 2
Test assessment embodiment 1, comparative example 1, comparative example 2 and 20wt% business platinum carbon are in 0.1mol/L KOH electrolyte
In hydrogen reduction performance.It is as follows described in testing procedure and result：
5mg embodiments 1, comparative example 1, comparative example 2 and 20wt% business platinum carbons sample are taken respectively adds 950 μ L isopropanols
(both volume ratios are 1 with the mixed solvent of water:1), and add 50 μ L mass concentrations be 5% Nafion as binding agent, surpass
Sound disperses or so 2 hours to obtain dispersed sample solution.Then the solution drop coating prepared described in 10 μ L is taken out straight
Footpath is in the rotating disk electrode (r.d.e) of 5mm, room temperature carries out performance characterization after drying film forming.
Saturation Ag/AgCl electrodes are chosen as reference electrode, graphite rod is used as to electrode, the rotating circular disk electricity of drop coating sample
Extremely the three-electrode system of working electrode, is 0.1mol/L KOH in oxygen saturation, electrolyte, and sweep speed is 5mV/s, rotation
Speed be 1600rpm under conditions of above-mentioned sample is tested.Experimental result is shown in Fig. 5, and embodiment 1 is made as seen from Figure 5
Standby high dispersive, the monatomic sample take-off potential of the iron of high activity site density and half wave potential all with 20wt% business platinum carbon phases
When respectively in 998mV and 845mV or so.Comparatively speaking, the gained sample take-off potential of comparative example 1 and half wave potential exist respectively
941mV and 802mV；The sample starting point of comparative example 2 position and half wave potential respectively in 928mV and 769mV, all well below embodiment
The hydrogen reduction performance of 1 gained sample.
Embodiment 3
Test assessment embodiment 1, comparative example 1, comparative example 2 and 20wt% business platinum carbon are in 0.1mol/L HClO4Electrolysis
Hydrogen reduction performance in liquid.It is as follows described in testing procedure and result：
5mg embodiments 1, comparative example 1, comparative example 2 and 20wt% business platinum carbons sample are taken respectively adds 950 μ L isopropanols
(both volume ratios are 1 with the mixed solvent of water:1), and add 50 μ L mass concentrations be 5% Nafion as binding agent, surpass
Sound disperses or so 2 hours to obtain dispersed sample solution.Then the solution drop coating prepared described in 10 μ L is taken out straight
Footpath is in the rotating disk electrode (r.d.e) of 5mm, room temperature carries out performance characterization after drying film forming.
Saturation Ag/AgCl electrodes are chosen as reference electrode, graphite rod is used as to electrode, the rotating circular disk electricity of drop coating sample
Extremely the three-electrode system of working electrode, is 0.1mol/L HClO in oxygen saturation, electrolyte4, sweep speed is 5mV/s, rotation
Rotary speed be 1600rpm under conditions of above-mentioned sample is tested.Experimental result is shown in Fig. 6, as seen from Figure 6 embodiment 1
The high dispersive of preparation, the monatomic sample take-off potential of the iron nitrogen of high activity site density and half wave potential respectively in 876mV and
658mV or so, it is more slightly worse than 20wt% business platinum carbon performances, but good to be obtained with properties of sample obtained by comparative example 2 than comparative example 1
It is many.
Compared to having more preferable stability for business platinum carbon, experiment shows sample obtained in the application simultaneously, in warp
Cross after general 1000 loop tests, the hydrogen reduction property of business platinum carbon will be decayed to and high dispersive iron obtained in the application
The suitable position of nitrogen-doped graphene catalyst.
Embodiment 4
A. the glucose of 0.25g and the dicyanodiamine of 5g are weighed and the two is dissolved in (attention in the deionized water of 200mL
Because solubility of the dicyanodiamine in water is relatively low, it is also required to increase the amount of water simultaneously when its quality is increased until reagent dissolves
Completely)；
B. measure the molar concentration that 2mL configures with liquid-transfering gun and be the liquor ferri trichloridi of 0.0125mol/L, and be added dropwise to
To in the glucose and dicyanodiamine solution for having dissolved；
C. the solution containing presoma that will have been configured is put on 80 DEG C of warm tables and is evaporated, then take out with mortar grinder into
Uniform powder, and put it into the quartz boat or corundum boat of suitable size and top is added a cover；
D. then Noah's ark is integrally placed in tube furnace, (nitrogen or argon gas) 800 DEG C of calcinings 2 are small under an inert atmosphere
When, and Temperature fall.
Obtained sample is tested using the method for testing of embodiment 2, Fig. 7 is as a result seen, as shown in Figure 7, it rises
Beginning current potential and half wave potential illustrate that its performance is slightly poor relative to sample obtained by embodiment 1 respectively in 961mV and 771mV, this
High while the electric conductivity at graphene-based bottom and bad mainly due to sample nitrogen content, it is excessively slow to cause its electron transfer rate,
Limit its catalytic reaction process.
Embodiment 5
A. the glucose of 0.25g and the dicyanodiamine of 5g are weighed and the two is dissolved in (attention in the deionized water of 200mL
Because solubility of the dicyanodiamine in water is relatively low, it is also required to increase the amount of water simultaneously when its quality is increased until reagent dissolves
Completely)；
B. measure the molar concentration that 2mL configures with liquid-transfering gun and be the liquor ferri trichloridi of 0.0125mol/L, and be added dropwise to
To in the glucose and dicyanodiamine solution for having dissolved；
C. the solution containing presoma that will have been configured is put on 80 DEG C of warm tables and is evaporated, then take out with mortar grinder into
Uniform powder, and put it into the quartz boat or corundum boat of suitable size and top is added a cover；
D. then Noah's ark is integrally placed in tube furnace, under an inert atmosphere (nitrogen or argon gas) 1000 DEG C of calcinings 2
Hour, and Temperature fall.
Obtained sample is tested using the method for testing of embodiment 2, Fig. 7 is as a result seen, as shown in Figure 7, it rises
Beginning current potential and half wave potential illustrate that its performance is suitable with the sample obtained by embodiment 1 respectively in 998mV and 854mV, or even half
Ripple potential value is bigger than embodiment 1, but carrying current value is less than normal, and this drops mainly due to sample nitrogen content because of high temperature
It is low at the same the electron transport ability at graphene-based bottom to be slightly better than 900 DEG C treatment samples.
Embodiment 6
A. the glucose of 0.25g and the dicyanodiamine of 5g are weighed and the two is dissolved in (attention in the deionized water of 200mL
Because solubility of the dicyanodiamine in water is relatively low, it is also required to increase the amount of water simultaneously when its quality is increased until reagent dissolves
Completely)；
B. the H that the molar concentration that 2mL configures is 0.0125mol/L is measured with liquid-transfering gun2PtCl6Solution, and be added dropwise to
In the glucose and dicyanodiamine solution that have dissolved；
C. the solution containing presoma that will have been configured is put on 80 DEG C of warm tables and is evaporated, then take out with mortar grinder into
Uniform powder, and put it into the quartz boat or corundum boat of suitable size and top is added a cover；
D. then Noah's ark is integrally placed in tube furnace, (nitrogen or argon gas) 900 DEG C of calcinings 2 are small under an inert atmosphere
When, and Temperature fall.
HAADF-STEM characterization methods are differentiated by STEM and time angstrom level and shows product pattern, the results are shown in Table 8, can by table 8
Know, Pt is uniformly supported on graphene-based bottom in the scattered form of atom level.
From above-described embodiment and comparative example, the monatomic graphene-based catalyst of load of transition metal prepared by the present invention
With activity higher and stability.
Above example is mainly with glucose as carbon source, and dicyanodiamine is nitrogen source, and iron chloride launches for source of iron, certainly not
What can be excluded is that carbon source is changed into the similar carbohydrate such as sucrose, or source of iron changes similar soluble ferric iron salt into and remains to obtain
Similar result.Embodiment 6 then further illustrates the universality of this method, and the application is also successfully prepared other transition
The monatomic catalyst of metal, cannot be exhaustive to all of implementation method here, and thus amplify out it is obvious
Among change or variation are still in the protection domain of preparation method of the present invention.
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (10)
1. the preparation method of the graphene-based catalyst of the monatomic load of a kind of high density transition metal, it is characterised in that including with
Lower step：
Nitrogenous precursor, carbon source and soluble transition metal salt are dissolved in water, is then dried by evaporation, grinds, calcined
To the monatomic graphene-based catalyst of load of high density transition metal.
2. preparation method according to claim 1, it is characterised in that specially：
A) nitrogenous precursor and carbon source are dissolved in water, is then mixed with soluble transition metal saline solution, obtained containing preceding
Drive the mixed solution of body；
B) by step A) the mixed solution evaporation drying containing presoma that obtains, obtain recrystallizing solid；
C) by above-mentioned recrystallization solid abrasive into powder；
D) above-mentioned powder is calcined under an inert atmosphere, the monatomic graphene-based catalyst of load of high density transition metal is obtained.
3. preparation method according to claim 1, it is characterised in that the nitrogenous precursor is dicyanodiamine.
4. preparation method according to claim 1, it is characterised in that the carbon source is organic carbohydrate.
5. preparation method according to claim 4, it is characterised in that the carbon source is glucose or sucrose.
6. preparation method according to claim 1, it is characterised in that the transition metal in the soluble transition metal salt
Atom is one or more in Fe, Co, Ni, Cu, Pt, Pd and Ru.
7. preparation method according to claim 1, it is characterised in that the monatomic load graphite of high density transition metal
In alkenyl catalyst, the mol ratio of C atoms, N atoms and metallic atom is 100：(9~20)：(0~2.2).
8. preparation method according to claim 1, it is characterised in that the temperature of the evaporation drying is 80 DEG C of ＜.
9. preparation method according to claim 1, it is characterised in that the temperature of the calcining is 750 DEG C of ＞, the calcining
Time be 1~3h.
10. the monatomic load of high density transition metal that prepared by the preparation method described in any one of claim 1~9 is graphene-based
Catalyst.
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