CN107469855A - A kind of preparation method of the monatomic catalyst of nitrogen-doped graphene carried metal - Google Patents
A kind of preparation method of the monatomic catalyst of nitrogen-doped graphene carried metal Download PDFInfo
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Abstract
A kind of preparation method of the monatomic catalyst of nitrogen-doped graphene carried metal, using disodium EDTA as compounding ingredient, stable complex is formed by ion-exchange reactions with metal ion in the liquid phase, it is sufficiently mixed uniformly with alkali metal salt after being evaporated, passes through the synchronous converting monatomic catalyst of metal for obtaining nitrogen-doped graphene and loading.Prepared catalyst has the two-dimentional morphology feature of ultra-thin large area, and thickness is 0.5~2nm, and the graphene number of plies is 1~8 layer, and content of metal can be applied to the energy, catalysis, medicine and biology etc. and catalyze and synthesize field between 0.01~10wt%.The present invention can be generally applicable to the synthesis of the monatomic catalyst of various metals, and resulting metal is monatomic can be good in graphenic surface, load capacity height, heat endurance by rivet securely.Operating procedure of the present invention is simple and safe, and cost is cheap, has the advantages that controllable preparation, largely synthesizes, and is adapted to industrialized production and scale application.
Description
Technical field
The invention belongs to monatomic catalyst preparation technical field, and in particular to one kind is synchronous using nitrogenous organic coordination compound
The converting method for preparing the monatomic catalyst of nitrogen-doped graphene carried metal.
Background technology
Material dimension and size are reduced, to synthesize the catalyst of nanocluster or single atomic dispersion, material can be significantly improved
The catalytic activity of material, and then obtain preferable catalytic efficiency.With the continuous development of nano material synthetic technology, the mankind exist
Rapid progress is achieved on material is multiple dimensioned, but synthesizes and regulates and controls in the structure for realizing the catalysis material of single atomic dispersion
And application aspect still faces significant challenge.Due to the monatomic unstability of itself, and in synthesis with easily gathering in application process
Collection is reunited, and up to the present, does not realize really simply efficiently largely synthesize heat-staple single atomic dispersion catalyst material yet.It is single
Atom dispersed catalyst is scantling least limit, and the upper limit (UL) of atom utilization can be reached in catalytic reaction, is
Most a kind of catalyst material of application prospect, and connection heterogeneous catalysis and the bridge of homogeneous catalysis, it is to realize homogeneously to urge
Change out-phase reliable approach.Although the existing method for more and more preparing single atomic dispersion catalyst is come out by successive report,
But these methods usually require accurate regulation and control synthesis, operating procedure is various, and yield is smaller, is only applicable under laboratory condition
Synthesis, and synthesized monatomic catalyst type out is only limitted to common several dvielements, and used carrier also rests on gold
Category or metal oxide this aspect, therefore the extensive use of single atomic dispersion catalyst is also limited to the synthesis skill of suitable material
Art.
Graphene is the individual layer two dimensional crystal structure arranged by carbon atom by hexagonal honeycomb shape, due to atomic level
Thickness, graphene show uniqueness electronic structure, can show novelty Macroscopic physical chemical characteristic.Due to compared with
High specific surface area, good electron conduction and unique graphitization two-dimension plane structure, graphene is considered as monatomic
The ideal carrier of dispersed catalyst, the great interest of researcher is caused recently.But the graphene that existing method is synthesized
All be the material of chemical stability, it is difficult to monometallic Atomic coordinate, even if existing researcher reports Atomic layer deposition method
The synthesis of graphene-supported Pt and Pd single atomic dispersions catalyst is realized, but content of metal is very low, metallic atom disperses
Poor, the monatomic limitednumber of property.
The content of the invention
The technical problems to be solved by the invention are：For at present simply magnanimity graphene-supported metal list original can not be prepared
The prior art situation of muonic catalysis agent, there is provided a kind of simple metal for efficiently largely preparing nitrogen-doped graphene load monatomic is urged
The universal method of agent, at the same there is prepared catalyst content of metal is very high, metal species cover wide, atom point
The advantages that scattered property is higher.
Technical scheme is as follows：
A kind of preparation method of the monatomic catalyst of nitrogen-doped graphene carried metal, it is characterised in that this method is included such as
Lower step：
1) organic compounds containing nitrogen disodium EDTA and metal salt are added in deionized water, the matter of the two
Ratio is measured 1000:1 to 100:Between 1, it is well mixed, prepares the aqueous solution that molar concentration is 0.001~0.5mol/L；Exist afterwards
0.5~6h of ion-exchange reactions is carried out at 40~120 DEG C, the complex stablized, is evaporated after drying and obtains complex solid
Powder；
2) complex solid powder that step 1) obtains is sufficiently mixed uniformly with alkali metal salt, complex solid powder and
The mass ratio of alkali metal salt is 1:5 to 1:Between 20, it is put into tube furnace, under an inert atmosphere, in 800~1200 DEG C of heat treatments
After 0.5~3h, room temperature is then naturally cooled to, obtains the monatomic catalyst of metal and alkali metal salt of nitrogen-doped graphene load
Mixture；
3) mixture for obtaining step 2) produces after the washing of acidic aqueous solution, pure water and absolute ethyl alcohol is dried successively
To the monatomic catalyst of metal of nitrogen-doped graphene load.
In above-mentioned technical proposal, metal in described catalyst it is monatomic for Ru, Rh, Pd, Re, Ir, Pt, Fe, Co,
Ni, Mn or Cu.The metal salt be respectively Ru, Rh, Pd, Re, Ir, Pt, Fe, Co, Ni, Mn or Cu chloride, sulfate,
One kind in nitrate and acetylacetonate.The alkali metal salt is sodium carbonate, potassium carbonate, sodium acid carbonate, sodium sulphate, sulfuric acid
Potassium, sodium chloride, potassium chloride, the salt-mixture of one or both of sodium nitrate and potassium nitrate above.Described inert gas is nitrogen
Gas or argon gas.
The technical characteristic of the present invention also resides in：The monatomic catalyst of nitrogen-doped graphene carried metal has two dimension micro-
Structure and morphology feature is seen, its thickness is 0.5~2nm, and the graphene number of plies is 1~8 layer, and content of metal is 0.01~10wt%%
Between.
The present invention compared with prior art, has the technique effect of advantages below and high-lighting：1. stone provided by the invention
The preparation method of the black monatomic catalyst of alkene carried metal be using disodium EDTA as compounding ingredient, in the liquid phase with gold
Category ion forms stable complex by ion-exchange reactions, then can obtain N doping graphite by synchronously converting
The monatomic catalyst of metal of alkene load.Ru, Rh, Pd, Re, Ir, Pt, Fe, Co, Ni, Mn, Cu in material are with monoatomic
Form is supported on graphenic surface, and metal species are more, and its preparation method is simple and practical, need to only change the species of metal precursor salt
Different metal single atomic dispersion catalyst is can be obtained by, synthetic method has general applicability.2. the present invention in Ru,
Rh, Pd, Re, Ir, Pt, Fe, Co, Ni, Mn, Cu element on graphene carrier stablized by nitrogen-atoms, there is good heat
Stability, and metallic atom loading concentrations are high.3. operating procedure of the present invention is simple and safe, cost is cheap, with controllable preparation, greatly
The advantages that amount synthesis, it is adapted to industrialized production and scale application.
Brief description of the drawings
Fig. 1 is that the monatomic catalyst of graphene-supported Pd prepared by embodiment 1 is electric in high angle annular dark field scanning transmission
Image under sub- microscope.
Fig. 2 is that the monatomic catalyst of graphene-supported Pt prepared by embodiment 2 is electric in high angle annular dark field scanning transmission
Image under sub- microscope.
Fig. 3 is that the monatomic catalyst of graphene-supported Pt prepared by embodiment 2 is electric in high angle annular dark field scanning transmission
Image under sub- microscope.
Fig. 4 is that the monatomic catalyst of graphene-supported Co prepared by embodiment 3 is electric in high angle annular dark field scanning transmission
Image under sub- microscope.
Fig. 5 is that the monatomic catalyst of graphene-supported Ni prepared by embodiment 4 is electric in high angle annular dark field scanning transmission
Image under sub- microscope.
Fig. 6 is that the monatomic catalyst of graphene-supported Fe prepared by embodiment 5 is electric in high angle annular dark field scanning transmission
Image under sub- microscope.
Embodiment
A kind of preparation method of monatomic catalyst of nitrogen-doped graphene carried metal provided by the invention, is with ethylenediamine
Sequestrene AA is compounding ingredient, and stable complex is formed by ion-exchange reactions with metal ion in the liquid phase, is evaporated
It is sufficiently mixed afterwards with alkali metal salt uniformly, passes through the synchronous converting monatomic catalysis of metal for obtaining nitrogen-doped graphene and loading
Agent, its preparation method mainly include the following steps that：
1) organic compounds containing nitrogen disodium EDTA and metal salt are added in deionized water, the two quality
Than 1000:1 to 100:Between 1, it is well mixed, the solution that molar concentration is 0.001~0.5mol/L is made；Then 40~
0.5~6h of ion-exchange reactions is carried out at 120 DEG C, the complex stablized, is evaporated after drying and obtains complex solid powder；
2) complex solid powder that step 1) obtains is sufficiently mixed uniformly with alkali metal salt, complex solid powder and
The mass ratio of alkali metal salt is 1:5 to 1:Between 20, it is put into tube furnace, (typically uses nitrogen or argon under an inert atmosphere
Gas), after 800~1200 DEG C are heat-treated 0.5~3h, complex is pyrolyzed to form carbon nitrogen free radical and metal ion, carbon nitrogen free radical
Reset in alkali metal salt reaction medium and form graphene, while nitrogen-atoms is inserted on graphene layer in a manner of chemical bond,
Forming coordinate bond with metal ion, to carry out stable metal monatomic, and metallic atom is uniformly supported on graphenic surface securely,
The monatomic catalyst of metal of nitrogen-doped graphene load is ultimately formed, room temperature is then naturally cooled to, obtains N doping graphite
The monatomic catalyst of metal of alkene load and the mixture of alkali metal salt；
3) mixture for obtaining step 2) produces after the washing of acidic aqueous solution, pure water and absolute ethyl alcohol is dried successively
To the monatomic catalyst of metal of nitrogen-doped graphene load.
In the above-mentioned technical solutions, it is Ru, Rh, Pd, Re, Ir, Pt, Fe, Co, Ni, Mn or Cu that the metal is monatomic.
The metal salt is respectively Ru, Rh, Pd, Re, Ir, Pt, Fe, Co, Ni, Mn or Cu chloride, sulfate, nitrate and acetyl
One kind in acetone salt.Alkali metal salt is sodium carbonate, potassium carbonate, sodium acid carbonate, sodium sulphate, potassium sulfate, sodium chloride, potassium chloride,
Salt-mixture more than one or both of sodium nitrate and potassium nitrate.
The monatomic catalyst of nitrogen-doped graphene carried metal prepared by methods described has two-dimentional morphology special
Sign, its thickness are 0.5~2nm, and for content of metal between 0.01~10wt%%, graphene carrier is the pyrolysis stone of N doping
Black alkene, the graphene number of plies are 1~8 layer.
Graphene-supported metal single atomic dispersion catalysis material of the present invention is a kind of brand-new by graphene
The stable single atomic dispersion material of nitrogen-atoms.The electronic structure that the nitrogen-atoms of doping can not only change graphene lifts its conduction
Property, while coordinate bond can be also formed with metallic atom to carry out stable metal monatomic, and metallic atom is uniformly supported on securely
Graphenic surface.The metal single atomic dispersion catalyst of nitrogen-doped graphene load provided by the present invention can greatly enrich gold
Belong to the species of monatomic catalyst, there is provided a kind of brand-new synthetic technology, be also the catalytic property of the research monatomic material of metal
Provide possibility.This patent proposes a kind of universal method for the monatomic catalyst of metal for preparing nitrogen-doped graphene load,
Active component in the monatomic catalyst of these metals is stable by nitrogen-atoms.
The embodiment enumerated below is it will be further appreciated that the present invention, but the present invention is not only limited to following examples.
Embodiment 1
The preparation of the graphene-supported monatomic catalyst of Pd：
Step 1,4g disodium EDTAs and 12mg tetrachloro-palladium acid sodium are added in deionized water, magnetic force stirs
Mix, 80 DEG C of reaction 2h, be then evaporated drying；
Step 2, the 4g products that step 1 obtains are sufficiently mixed uniformly with 30g sodium carbonate, be put into tube furnace, indifferent gas
Under atmosphere, after 800 DEG C of heat treatment 3h, room temperature is naturally cooled to, obtains black mixture；
Step 3, black mixture step 2 obtained is successively by 1M hydrochloric acid solution, pure water and absolute ethyl alcohol washing
Just the monatomic catalyst of metal Pd of nitrogen-doped graphene load is obtained after drying.It is mono- former for graphene-supported Pd as shown in Figure 1
Image of the muonic catalysis agent under high angle annular dark field scanning transmission electron microscope, bright metal Pd is monatomic equably to be divided
Graphenic surface is dispersed in, Metal Supported concentration is higher.
Embodiment 2
The preparation of the graphene-supported monatomic catalyst of Pt：
Step 1,6g disodium EDTAs and 5.6mg potassium platinic chlorides are added in deionized water, magnetic force stirs
Mix, 80 DEG C of reaction 6h, be then evaporated drying；
Step 2, the 6g products that step 1 obtains are sufficiently mixed uniformly with 30g sodium sulphate, be put into tube furnace, indifferent gas
Under atmosphere, after 850 DEG C of heat treatment 2h, room temperature is naturally cooled to, obtains black mixture；
Step 3, black mixture step 2 obtained is washed by 0.5M sulfuric acid solution, pure water and absolute ethyl alcohol successively
Wash the monatomic catalyst of Pt metal that nitrogen-doped graphene load is just obtained after drying.It is mono- to be illustrated in figure 2 graphene-supported Pt
Image of the catalyst atom under transmission electron microscope, overall pattern are ultra-thin two-dimension nanostructured, have graphene typical case
Feature.Fig. 3 show the monatomic catalyst of graphene-supported Pt under high angle annular dark field scanning transmission electron microscope
Image, bright Pt metal is monatomic to be evenly dispersed in graphenic surface, and Metal Supported concentration is higher.
Embodiment 3
The preparation of the graphene-supported monatomic catalyst of Co：
Step 1,2g disodium EDTAs and 7.6mg cobalt nitrates are added in deionized water, magnetic agitation, 40
DEG C reaction 2h, be then evaporated drying；
Step 2, the 2g products that step 1 obtains are sufficiently mixed uniformly with 40g sodium sulphate, be put into tube furnace, indifferent gas
Under atmosphere, after 900 DEG C of heat treatment 1h, room temperature is naturally cooled to, obtains black mixture；
Step 3, black mixture step 2 obtained is successively by 1M hydrochloric acid solution, pure water and absolute ethyl alcohol washing
Just the monatomic catalyst of metal Co of nitrogen-doped graphene load is obtained after drying.It is mono- former to be illustrated in figure 4 graphene-supported Co
Image of the muonic catalysis agent under high angle annular dark field scanning transmission electron microscope, bright metal Co is monatomic equably to be divided
It is dispersed in graphenic surface.
Embodiment 4
The preparation of the graphene-supported monatomic catalyst of Ni：
Step 1,8g disodium EDTAs and 13mg nickel chlorides are added in deionized water, magnetic agitation, 80
DEG C reaction 0.5h, be then evaporated drying；
Step 2, the 8g products that step 1 obtains are sufficiently mixed uniformly with 48g potassium carbonate, be put into tube furnace, indifferent gas
Under atmosphere, after 950 DEG C of heat treatment 0.5h, room temperature is naturally cooled to, obtains black mixture；
Step 3, black mixture step 2 obtained is successively by 1M hydrochloric acid solution, pure water and absolute ethyl alcohol washing
Just the monatomic catalyst of W metal of nitrogen-doped graphene load is obtained after drying.It is mono- former to be illustrated in figure 5 graphene-supported Ni
Image of the muonic catalysis agent under high angle annular dark field scanning transmission electron microscope, bright W metal is monatomic equably to be divided
Graphenic surface is dispersed in, Metal Supported concentration is higher.
Embodiment 5
The preparation of the graphene-supported monatomic catalyst of Fe：
Step 1,7g disodium EDTAs and 8.6mg iron chloride are added in deionized water, magnetic agitation, 80
DEG C reaction 2h, be then evaporated drying；
Step 2, the 7g products that step 1 obtains are sufficiently mixed uniformly with 35g sodium nitrate, be put into tube furnace, indifferent gas
Under atmosphere, after 1000 DEG C of heat treatment 0.5h, room temperature is naturally cooled to, obtains black mixture；
Step 3, black mixture step 2 obtained is successively by 1M hydrochloric acid solution, pure water and absolute ethyl alcohol washing
Just the monatomic catalyst of metal Fe of nitrogen-doped graphene load is obtained after drying.It is mono- former to be illustrated in figure 6 graphene-supported Fe
Image of the muonic catalysis agent under high angle annular dark field scanning transmission electron microscope, bright metal Fe is monatomic equably to be divided
It is dispersed in graphenic surface.
Embodiment 6
The preparation of the graphene-supported monatomic catalyst of Rh：
Step 1,9g disodium EDTAs and 5.6mg chlordene rhodium acid ammoniums are added in deionized water, magnetic force stirs
Mix, 80 DEG C of reaction 2h, be then evaporated drying；
Step 2, the 9g products that step 1 obtains are sufficiently mixed uniformly with 45g sodium nitrate, be put into tube furnace, indifferent gas
Under atmosphere, after 900 DEG C of heat treatment 0.5h, room temperature is naturally cooled to, obtains black mixture；
Step 3, black mixture step 2 obtained is successively by 1M hydrochloric acid solution, pure water and absolute ethyl alcohol washing
Just the monatomic catalyst of metal Rh of nitrogen-doped graphene load is obtained after drying.
Embodiment 7
The preparation of the graphene-supported monatomic catalyst of Ru：
Step 1,5g disodium EDTAs and 4.3mg hydration ruthenium hydrochloride sodium are added in deionized water, magnetic force
Stirring, 100 DEG C of reaction 2h, is then evaporated drying；
Step 2, the 5g products that step 1 obtains are sufficiently mixed uniformly with 45g sodium nitrate, be put into tube furnace, indifferent gas
Under atmosphere, after 800 DEG C of heat treatment 2h, room temperature is naturally cooled to, obtains black mixture；
Step 3, black mixture step 2 obtained is successively by 1M hydrochloric acid solution, pure water and absolute ethyl alcohol washing
Just the monatomic catalyst of metal Ru of nitrogen-doped graphene load is obtained after drying.
Embodiment 8
The preparation of the graphene-supported monatomic catalyst of Ir：
Step 1,7g disodium EDTAs and 5.7mg potassium hexachloroiridates are added in deionized water, magnetic agitation,
80 DEG C of reaction 4h, are then evaporated drying；
Step 2, the 7g products that step 1 obtains are sufficiently mixed uniformly with 35g sodium carbonate, be put into tube furnace, indifferent gas
Under atmosphere, after 1100 DEG C of heat treatment 0.5h, room temperature is naturally cooled to, obtains black mixture；
Step 3, black mixture step 2 obtained is successively by 1M hydrochloric acid solution, pure water and absolute ethyl alcohol washing
Just the monatomic catalyst of metal Ir of nitrogen-doped graphene load is obtained after drying.
Claims (6)
1. a kind of preparation method of the monatomic catalyst of nitrogen-doped graphene carried metal, it is characterised in that this method includes as follows
Step：
1) organic compounds containing nitrogen disodium EDTA and metal salt are added in deionized water, ethylenediamine tetra-acetic acid
The mass ratio of disodium salt and metal salt is 1000:1 to 100:Between 1, be well mixed, prepare molar concentration be 0.001~
The 0.5mol/L aqueous solution；0.5~6h of ion-exchange reactions is carried out at 40~120 DEG C afterwards, the complex stablized, is steamed
Complex solid powder is obtained after drying；.
2) the complex solid powder that step 1) obtains is sufficiently mixed uniformly with alkali metal salt, complex solid powder and alkali gold
The mass ratio for belonging to salt is 1:5 to 1:Between 20, it is put into tube furnace, under an inert atmosphere, 0.5 is heat-treated in 800~1200 DEG C
After~3h, room temperature is then naturally cooled to, obtains the metal monatomic catalyst and alkali metal salt of nitrogen-doped graphene load
Mixture；
3) mixture for obtaining step 2) obtains nitrogen after the washing of acidic aqueous solution, pure water and absolute ethyl alcohol is dried successively
The monatomic catalyst of metal of doped graphene load.
2. the preparation method of the monatomic catalyst of nitrogen-doped graphene carried metal according to claim 1, its feature exist
In：Monatomic metal in the catalyst is Ru, Rh, Pd, Re, Ir, Pt, Fe, Co, Ni, Mn or Cu.
3. the preparation method of the monatomic catalyst of nitrogen-doped graphene carried metal according to claim 1, its feature exist
In：The metal salt be respectively Ru, Rh, Pd, Re, Ir, Pt, Fe, Co, Ni, Mn or Cu chloride, sulfate, nitrate and
One kind in acetylacetonate.
4. the preparation method of the monatomic catalyst of nitrogen-doped graphene carried metal according to claim 1, its feature exist
In：The alkali metal salt be sodium carbonate, potassium carbonate, sodium acid carbonate, sodium sulphate, potassium sulfate, sodium chloride, potassium chloride, sodium nitrate and
Salt-mixture more than one or both of potassium nitrate.
5. the preparation method of the monatomic catalyst of nitrogen-doped graphene carried metal according to claim 1, its feature exist
In：Described inert gas is nitrogen or argon gas.
6. the preparation of the monatomic catalyst of nitrogen-doped graphene carried metal according to claim 1-5 any claims
Method, it is characterised in that：The two-dimentional morphology feature that the catalyst has, thickness are 0.5~2nm, and graphene is heat
Graphene is solved, the number of plies of graphene is 1~8 layer, and content of metal is between 0.01~10wt%%.
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