CN109300701A - A kind of efficient electric catalyst composite and its preparation method and application based on hierarchical porous structure graphene aerogel - Google Patents
A kind of efficient electric catalyst composite and its preparation method and application based on hierarchical porous structure graphene aerogel Download PDFInfo
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention discloses a kind of efficient electric catalyst composite and its preparation method and application based on hierarchical porous structure graphene aerogel.The preparation method obtains surface with the graphene oxide layer dispersion liquid abundant through meso-hole structure the following steps are included: to graphene oxide dispersion progress oxide etch；Reducing agent is added and carries out reduction assembling, obtains the three-dimensional grapheme hydrogel with multi-stage artery structure；Above-mentioned three-dimensional grapheme hydrogel is impregnated with metal front liquid solution, using hydro-thermal method or high temperature pyrolytic cracking (HTP), the efficient electric catalyst composite is can be obtained in freeze-drying.This special hierarchical porous structure sufficiently exposes the active site of catalyst, substantially increases electrolyte to the wellability of catalyst activity substance, accelerates the mass transfer in catalytic process inside system；In addition it avoids electro catalytic activity caused by support body material fails because of electrochemical oxidation and loses problem, show excellent catalytic activity, high catalytic stability and fast mass transfer characteristic.
Description
Technical field
The invention belongs to Application of micron and elctro-catalyst synthesis and preparation technical fields.More particularly, to one
Efficient electric catalyst composite and its preparation method and application of the kind based on hierarchical porous structure graphene aerogel.
Background technique
Noble metal platinum (Pt), golden (Au), silver (Ag) and palladium (Pd) etc. are the electrocatalyst materials being most widely used at present
One of, but the disadvantages such as its is at high cost, reserves are few, stability is bad seriously limit the extensive of such noble metal electrocatalyst
Using.For this problem, there are two types of the schemes that generally use at present: 1) developing catalytic activity can be with precious metal based catalysts
The non-precious metal catalyst material to compare favourably, although living by the catalysis that such non-precious metal catalyst can be improved in structure design
Property, but it still obtains unsatisfactory catalytic activity and stability, strongly limits it and replaces noble metal catalyst
Large-scale application it is potentially possible；2) nano-alloyed composite electrocatalyst is prepared based on noble metal, passes through accurate structure
Control, the sufficiently active site of exposure noble metal, greatly improve the unit mass catalytic activity of noble metal, to greatly reduce
The dosage of noble metal catalyst.Compared with the first scheme, the noble metal electrocatalyst material of alloying possesses higher electrochemistry
Catalytic activity, lower overpotential, better stability, with more excellent electrochemical catalysis comprehensive performance and more extensively
Application prospect.
Because the agglomeration traits in preparation process and the curing reunion in electrochemical process, electrochemical corrosion leach problem,
In practical applications, the excellent synthesis catalytic performance of the noble metal nano alloy catalyst of alloying is often unable to get complete hair
It waves.The introducing of carbon carrier can function well as sufficiently exposure, stable and activating catalytic active site effect, assign final
Composite catalyst preferably integrate catalytic performance.Graphene has excellent lead as high-graphitized two-dimentional carbon material
Electrically, stability and mechanical performance, while there is high carrier mobility and big specific surface area, from structure and intrinsic property
It is ideal catalyst carrier material for upper.However, graphene is carried as elctro-catalyst due to attribute of two-dimensional material itself
When body, often it is faced with serious interlayer and stacks agglomeration traits, and then slow mass transfer rate and active site is caused to be blanked
The problems such as.
The graphene aerogel by the self assembly preparation of graphene sheet layer with three-dimensional net structure is to solve graphene
Lamella is used as the effective means of incident agglomeration traits when carrier, and can provide express passway for electron-transport.Moreover,
It, cannot be inside entire aeroge since the mass transfer of conventional graphite alkene aeroge network internal suffers from the restriction effect of hole wall
Quick mass transport process is formed, compared with conventional graphite alkene aeroge, the noble metal of three-dimensional structure graphene aerogel support type
There are also very big rooms for promotion for the synthesis electrocatalysis characteristic of nanometer alloy catalyst material.Three-dimensional grapheme load is obtained at present to receive
The also rare report of the composite material of rice grain, and it is difficult the structure for making Nanoalloy even particulate dispersion in three-dimensional grapheme
In, catalytic activity is undesirable, and in addition its support body material is easy to cause electro catalytic activity to be lost because of electrochemical oxidation failure.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the defect of the above-mentioned prior art and deficiencies, provide one kind and have both fast biography
The efficient electric catalyst composite based on hierarchical porous structure graphene aerogel of matter, high activity and high stability.
The first purpose of the invention is to provide a kind of efficient elctro-catalysts based on hierarchical porous structure graphene aerogel
The preparation method of composite material.
A second object of the present invention is to provide the efficient electric catalyst composites for using the above method to be prepared.
Third object of the present invention is to provide above-mentioned efficient electric catalyst composite as or prepare electrode material
In application.
Fourth object of the present invention is to provide a kind of catalyst carrier comprising above-mentioned efficient electric catalyst composite.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of the efficient electric catalyst composite based on hierarchical porous structure graphene aerogel, including following step
It is rapid:
S1. dispersion removing after graphite oxidation is obtained into evenly dispersed graphene oxide dispersion into solvent；Utilize oxidation
Agent performs etching pore-forming processing to graphene oxide dispersion, obtains surface with the graphite oxide abundant through meso-hole structure
Alkene lamella dispersion liquid；
S2. reducing agent is added and carries out reduction assembling, obtains the three-dimensional grapheme hydrogel with multi-stage artery structure；
S3. above-mentioned three-dimensional grapheme hydrogel is impregnated with metal front liquid solution to obtain using hydro-thermal method or high temperature pyrolytic cracking (HTP)
To the supported nano-gold category of hierarchical porous structure or the graphene composite hydrogel of nano metal alloy catalyst, freeze-drying is obtained
To the efficient electric catalyst composite.
The present invention is designed by introducing mesoporous structure on macroporous structure graphene aerogel skeleton, is had
The hierarchical porous structure graphene aerogel carrier of fast mass transfer and high activity；Continue on the aeroge skeleton of this hierarchical porous structure
Supported porous nano metal or nano metal alloy composite catalyst plays stable dispersion catalyst nano-particles, sufficiently sudden and violent
While revealing active site, ensure rapid mass transfer inside system, play a very good protection to non pinetallic nano particle, sufficiently
Catalyst electrochemical catalysis performance is quick caused by avoiding the corrosion dissolution in electrochemistry maturing process and electrochemical process
Decaying；It finally obtains the hierarchical porous structure nano metal/graphene aerogel for having both fast mass transfer, high activity and high stability or receives
Rice metal alloy/graphene aerogel elctro-catalyst composite material.
Preferably, in step S3, in order to continue to introduce porous nano metal or more on graphene hydrogel three-dimensional skeleton
Hole nano metal alloy particle carries out solvent displacement, gold as needed to three-dimensional grapheme hydrogel obtained in step S2
Belong to synthetic system or metal alloy synthetic system, selects one of DMSO, NMP, ethyl alcohol, DMF, ethylene glycol or glycerine or several
Kind organic solvent carries out solvent displacement, obtains the multi-stage porous graphene hydrogel of target solvent filling.
Preferably, in step S1, the lamellar spacing of the graphene oxide dispersion is 1~10 layer of carbon atom.
Preferably, the concentration of the graphene oxide dispersion is 0.1~20 mg/mL.
It is highly preferred that the concentration of the graphene oxide dispersion is 2~10 mg/mL.Such as 2 mg/mL, 3 mg/mL,
4 mg/mL, 5 mg/mL, 6 mg/mL, 7 mg/mL, 8 mg/mL, 9 mg/mL, 10 mg/mL etc..
Preferably, in step S1, the quality volume of the oxidant and graphene oxide dispersion be 0.1~10 g:1~
100 mL.Such as 0.1 g:1 mL, 1 g:10 mL, 5 g:40 mL, 10 g:50 mL, 10 g:90 mL etc..
Preferably, the oxidant in the step S1 is selected from the potassium ferricyanide, iron chloride, hydrogen peroxide, potassium permanganate or chloric acid
One or more of potassium.
Preferably, in step S1, the dispersion stripping means is stirred selected from ball milling dispersion, mechanical stirring, ultrasonic disperse, magnetic force
It mixes or at least one of high-pressure homogeneous dispersion stripping means.
Preferably, the solvent in the step S1 is selected from water, acetone, ethyl alcohol, methanol, propyl alcohol, isopropanol, the tert-butyl alcohol, second
One or more of glycol, DMSO, DMF, THF or pyridine.
Preferably, in step S2, the condition of the reduction assembling are as follows: 60~90 DEG C of 0.5~6 h of reaction.
It is highly preferred that in step S2, the condition of the reduction assembling are as follows: 90 DEG C of 3 h of reaction.
Preferably, in step S2, the additive amount of the reducing agent is the 0.01%~5% of graphene oxide layer dispersion liquid.
It is highly preferred that in step S2, the additive amount of the reducing agent be graphene oxide layer dispersion liquid 0.01%~
1%。
Preferably, the reducing agent in the step S2 be selected from sodium borohydride, hydroiodic acid, hydrazine hydrate, ascorbic acid, ammonium hydroxide or
One or more of ethylenediamine.
Preferably, in step S3, the quality of presoma and three-dimensional grapheme hydrogel in the metal front liquid solution
Than for 1:20~1000.Such as 1:20,1:50,1:100,1:200,1:300,1:450,1:500,1:600,1:900,1:1000
Deng.
Preferably, the soaking time is 6~48 h.Such as 6 h, 10 h, 12 h, 15 h, 20 h, 24 h, 30 h, 36
H, 40 h, 48 h etc..
Preferably, in the efficient electric catalyst composite, the type of nano metal or nano metal alloy be selected from Pt,
Pd, Au, Ag, Ni, Fe, Co or Cu etc..Can arbitrarily be arranged in pairs or groups type and proportion, the particle ruler of nano metal or nano metal alloy
Very little is 3~15 nm, and is evenly distributed on the skeleton of graphene hydrogel.Meanwhile the ratio table of the elctro-catalyst composite material
Area is high, has cellular structure abundant, high electron-transport and quality transmission rate, prevents graphene and nano particle
Reunion, the load capacity of metal or metal alloy catalyst is high, and catalytic performance is excellent, and more traditional three-dimensional grapheme aeroge
Support type composite electro catalytic agent material shows lower overpotential (energy-efficient), can need to select according to different
The component of catalyst.
Preferably, the metal precursor solution type is a kind of and a variety of in Pt, Pd, Au, Ag, Ni, Fe, Co, Cu；
If alloy, then the proportion between metal front liquid solution can arbitrarily regulate and control.
It is highly preferred that the nano metal alloy is Platinum Nanoparticles nickel metal alloy.
Preferably, the condition of the high temperature pyrolysis reaction are as follows: 300~500 DEG C of 3~8 h of reaction.
It is highly preferred that the condition of the high temperature pyrolysis reaction are as follows: 350~450 DEG C of 4~6 h of reaction.
Preferably, the condition of the hydro-thermal reaction are as follows: 160~200 DEG C of 3~24 h of reaction.
It is highly preferred that the condition of the hydro-thermal reaction are as follows: 170~190 DEG C of 6~12 h of reaction.
The freeze-drying is orientation freeze-drying or non-directional freeze-drying, and cryogenic temperature is -196~-5 DEG C, freezing
Time is 0.1~10 h；Drying temperature is 0~15 DEG C, and dry vacuum degree is 1~20 Pa, and drying time is 12~72 h.
The efficient electric catalyst composite based on hierarchical porous structure graphene aerogel that the above method is prepared,
Within protection scope of the present invention.
Elctro-catalyst composite material pattern of the invention is complicated, obtained hierarchical porous structure noble metal nano gold/graphite
The specific surface area of alkene aeroge elctro-catalyst composite material is high, has cellular structure abundant, and the load of noble metal catalyst
Amount is up to 20 wt% or more.For being catalyzed formic acid and decompose, unit mass and unit area catalytic activity are up to 650 respectively
MA/mg and 4.55 mA/cm2, and more traditional aerogel carried type composite electro catalytic agent material of three-dimensional grapheme show it is lower
Overpotential (energy-efficient).
The efficient electric catalyst composite has three-dimensional continuous hierarchical porous structure；1.08~1.85 cm of Kong Rongwei
³/g；The aperture of macropore is 1~100 μm, and mesoporous aperture is 2~50 nm；Specific surface area is 400~600 m2/g。
When the specific surface area of the efficient electric catalyst composite is 400 m2When/g, the load capacity of catalyst is at least
For 20 wt%.
Above-mentioned efficient electric catalyst composite can be used as electrode material applied to lithium ion battery and super capacitor etc.
In manufacture.Correspondingly, above-mentioned efficient electric catalyst composite as or prepare application in electrode material, also in the present invention
Protection scope within.
The present invention also provides a kind of catalyst carriers comprising above-mentioned efficient electric catalyst composite, have preferable
Stability and excellent catalytic activity.
Compared with prior art, the invention has the following advantages:
(1) present invention introduces the meso-hole structure largely penetrated through on graphene aerogel skeleton, has well solved traditional three
Tie up the problem that graphene aerogel is caused catalyst material internal mass transfer slow by the inhibition of hole wall.
(2) present invention by with hierarchical porous structure graphene aerogel and itself have porous structure nano metal or
Nano metal alloy is combined, and is effectively formed the elctro-catalyst composite material with hierarchical porous structure, is sufficiently exposed and urge
Agent active site greatly improves the catalytic activity of catalyst, accelerates the mass transfer in catalytic process inside system；And
And in recombination process, using simple and easy hydro-thermal in situ synthesis, the composite material that more common solution blended process obtains,
The dispersion of porous nano metal or nano metal alloy is more uniform, it is between hierarchical porous structure graphene aerogel skeleton
Binding force it is stronger, avoid the curing that falls off in long circulating use process, further increase the stability of catalyst.
(3) the very high multi-stage porous graphene aerogel skeleton of degree of graphitization of the present invention can be used as during electro-catalysis
Outstanding support body material, avoid support body material because electrochemical oxidation failure caused by electro catalytic activity lose ask
Topic；In electrocatalytic reaction, such as Oxidation of Formic Acid, while it is special to show excellent catalytic activity, high catalytic stability and fast mass transfer
Property.
(4) present invention has reaction process simple, and reaction step is few, and reaction time is short, the advantages such as reproducible, urges in electricity
Agent field has a good application prospect and wide development space.
Detailed description of the invention
Fig. 1 is the transmission electron microscope picture of the porous graphene oxide layer of the present invention.
Fig. 2 is the digital photograph of multi-stage porous graphene hydrogel of the present invention.
Fig. 3 is the transmission electricity for the multi-stage porous noble metal nano alloy/graphite alkene aeroge composite catalyst that the present invention obtains
Mirror and scanning electron microscopic picture.
Fig. 4 is the nitrogen DFT for the multi-stage porous noble metal nano alloy/graphite alkene aeroge composite catalyst that the present invention obtains
Pore size distribution figure.
Fig. 5 is that the formic acid of multi-stage porous noble metal nano alloy/graphite alkene aeroge composite catalyst prepared by the present invention is urged
Change performance map.
Fig. 6 is that the timing of multi-stage porous noble metal nano alloy/graphite alkene aeroge composite catalyst prepared by the present invention is pacified
Train curve.
Fig. 7 is multi-stage porous noble metal nano alloy/graphite alkene aeroge composite catalyst prepared by the present invention and traditional stone
Comparison diagram of the black aerogel carried porous noble metal nano alloy composite catalyst of alkene to Catalyzed by Formic Acid performance.
Specific embodiment
The present invention is further illustrated below in conjunction with Figure of description and specific embodiment, but embodiment is not to the present invention
It limits in any form.Unless stated otherwise, the present invention uses reagent, method and apparatus routinely try for the art
Agent, method and apparatus.
Unless stated otherwise, following embodiment agents useful for same and material are commercially available.
The synthesis of 1 multi-stage porous noble metal nano alloy/graphite alkene aeroge composite catalyst of embodiment
1, it is prepared by the following method multi-stage porous noble metal hole Nanoalloy/graphene aerogel composite catalyst, including following
Step:
(1) synthetic surface has the graphene oxide layer dispersion liquid of abundant meso-hole structure:
Synthesis graphene oxide dispersion: 150 are dispersed by 5 g natural flake graphites, 5 g sodium nitrate and 15 g potassium permanganate
In the mL concentrated sulfuric acid, after being stirred to react 10 h, after being warming up to 95 DEG C of 0.5 h of reaction, stands, remove supernatant liquor, precipitating is centrifuged
Washing is removed in aqueous solvent by 15 min of ultrasonic disperse for several times to being in neutrality, evenly dispersed oxidation can be obtained
Graphene dispersing solution；
Etching pore-forming processing: 100 mL of graphene oxide solution of 5 mg/mL is taken, 2.5 g of oxidant iron chloride is added, boils 3
H performs etching pore-forming and handles, and after centrifuge washing 2~4 times, the graphene oxide sheet that surface has abundant meso-hole structure can be obtained
Layer dispersion liquid；
(2) synthesis has the three-dimensional grapheme hydrogel of multi-stage artery structure:
It takes 3 surfaces mg/mL to have 100 mL of graphene oxide layer dispersion liquid of abundant meso-hole structure, 3 mL hydroiodic acids is added
The 3% of graphene oxide layer dispersion liquid (hydroiodic acid additional amount be) after 90 DEG C of 3 h of reaction, can be obtained with multistage pore canal knot
The three-dimensional grapheme hydrogel of structure；
(3) multi-stage porous noble metal hole Nanoalloy/graphene aerogel composite catalyst is synthesized:
After a large amount of clear water washing by soaking of three-dimensional grapheme hydrogel, it is placed in the mixed solution of chloroplatinic acid and nickel chloride and selects
Ethyl alcohol carry out solvent replace 6 h, wherein the presoma in metal front liquid solution (mixed solution of chloroplatinic acid and nickel chloride) with
Three dimensional hydrogel mass ratio 1:20；
After the completion of to be replaced, global transfer is warming up to 170 DEG C and carries out 6 h of reaction, eventually pass through washing and freezing into water heating kettle
It is dry that (wherein, cryogenic temperature is -5 DEG C, and cooling time is 10 h；Drying temperature is 15 DEG C, and dry vacuum degree is 1 Pa, dry
Time h), can be obtained multi-stage porous noble metal nano alloy/graphite alkene aeroge composite catalyst (i.e. Platinum Nanoparticles nickel gold for 72
Belong to alloy/graphite alkene aeroge composite catalyst).
2, conventional precious metal Nanoalloy/graphene aerogel composite catalyst preparation
In order to carry out performance comparison, we are prepared for compound the urging of the supported porous nano metal alloy of traditional graphene aerogel
Agent material, preparation method and the preparation of above-mentioned multi-stage porous noble metal hole Nanoalloy/graphene aerogel composite catalyst
Method is almost the same, in addition to not performing etching pore-forming processing to graphene oxide layer, i.e., do not carry out that iron chloride is added and boiling
Step.
3, result
(1) the present embodiment is obtained porous graphene oxide layer (as shown in Figure 1) by oxide etch, is added 90 DEG C of hydroiodic acid
The multi-stage porous graphene hydrogel (as shown in Figure 2) that 3 h of lower reaction are obtained.
(2) the present embodiment obtains the metal nano alloy/graphite alkene composite aerogel of hierarchical porous structure, transmission electron microscope picture
As shown in figure 3, having three-dimensional continuous hierarchical porous structure, it is 1.85 cm3/g that mesoporous, which holds, and the aperture of macropore is about 50 μm,
Mesoporous aperture is about 20 nm；Its specific surface area is up to 517.4 m2/ g(is as shown in Figure 4), there is cellular structure abundant, and
The load capacity of porous noble metal nano alloy is up to 20 wt% or more.
(3) the present embodiment obtains the metal nano alloy/graphite alkene composite aerogel of hierarchical porous structure, to be catalyzed formic acid point
For solution, unit mass and unit area catalytic activity are up to 580 mA/mg and 4.0 mA/cm respectively2(as shown in Figure 4),
It is as many as 6 times of commercial pallium-on-carbon (20 wt%) catalyst, and keeps extremely excellent electrochemical stability (such as Fig. 6 institute
Show).
(4) the present embodiment obtains metal nano alloy/graphite alkene composite aerogel (the multi-stage porous noble metal of hierarchical porous structure
Nanoalloy/graphene aerogel composite catalyst), the aerogel carried type composite electrocatalyst material of more traditional three-dimensional grapheme
Material (conventional precious metal Nanoalloy/graphene aerogel composite catalyst) shows lower overpotential and higher catalysis is lived
Property (as shown in Figure 7).
The synthesis of 2 multi-stage porous noble metal nano alloy/graphite alkene aeroge composite catalyst of embodiment
1, preparation method
The preparation method other conditions of the present embodiment catalyst with embodiment 1, the difference is that:
(1) reducing agent is sodium borohydride；
(2) condition of hydro-thermal reaction are as follows: 180 DEG C of 6 h of hydro-thermal reaction.
2, result
(1) the present embodiment obtains the metal nano alloy/graphite alkene composite aerogel of hierarchical porous structure, and specific surface area is up to
510 m2/ g has cellular structure abundant, and the load capacity of porous noble metal nano alloy is up to 20 wt% or more.
(3) the present embodiment obtains the metal nano alloy/graphite alkene composite aerogel of hierarchical porous structure, to be catalyzed formic acid point
For solution, unit mass and unit area catalytic activity are up to 520 mA/mg and 3.55 mA/cm respectively2, it is that commercial carbon carries
As many as nearly 6 times of platinum (20 wt%) catalyst, and keep extremely excellent electrochemical stability.
(4) the present embodiment obtains metal nano gold/graphene composite aerogel of hierarchical porous structure, more traditional three-dimensional
Graphene aerogel support type composite electro catalytic agent material shows lower overpotential and higher catalytic activity.
The synthesis of 3 multi-stage porous noble metal nano alloy/graphite alkene aeroge composite catalyst of embodiment
1, preparation method
The preparation method other conditions of the present embodiment catalyst with embodiment 2, the difference is that:
(1) reducing agent is ascorbic acid；
(2) condition of hydro-thermal reaction are as follows: 180 DEG C of 12 h of hydro-thermal reaction.
2, result
(1) the present embodiment obtains the metal nano alloy/graphite alkene composite aerogel of hierarchical porous structure, and specific surface area is up to
450 m2/ g has cellular structure abundant, and the load capacity of porous noble metal nano alloy is up to 20 wt% or more.
(3) the present embodiment obtains the metal nano alloy/graphite alkene composite aerogel of hierarchical porous structure, to be catalyzed formic acid point
For solution, unit mass and unit area catalytic activity are up to 510 mA/mg and 3.55 mA/cm respectively2, it is that commercial carbon carries
As many as 5 times of platinum (20 wt%) catalyst, and keep extremely excellent electrochemical stability.
(4) the present embodiment obtains metal nano gold/graphene composite aerogel of hierarchical porous structure, more traditional three-dimensional
Graphene aerogel support type composite electro catalytic agent material shows lower overpotential and higher catalytic activity.
The synthesis of 4 multi-stage porous noble metal nano alloy/graphite alkene aeroge composite catalyst of embodiment
1, preparation method
The preparation method other conditions of the present embodiment catalyst with embodiment 2, the difference is that:
After the completion of replacing, the hierarchical porous structure graphene hydrogel directly freezed with metal front liquid solution is dry, then
Under the protection of argon gas by obtained composite aerogel, 500 DEG C of 3 h of high-temperature process, prepare multi-stage porous using high temperature pyrolytic cracking (HTP)
Nano metal/graphene aerogel composite catalyst.
2, result
(1) the present embodiment obtains the metal nano alloy/graphite alkene composite aerogel of hierarchical porous structure, and specific surface area is up to
405 m2/ g has cellular structure abundant, and the load capacity of porous noble metal nano alloy is up to 20 wt% or more.
(3) the present embodiment obtains the metal nano alloy/graphite alkene composite aerogel of hierarchical porous structure, to be catalyzed formic acid point
For solution, unit mass and unit area catalytic activity are up to 555 mA/mg and 3.7 mA/cm respectively2, it is commercial pallium-on-carbon
As many as nearly 6 times of (20 wt%) catalyst, and keep extremely excellent electrochemical stability.
(4) the present embodiment obtains metal nano gold/graphene composite aerogel of hierarchical porous structure, more traditional three-dimensional
Graphene aerogel support type composite electro catalytic agent material shows lower overpotential and higher catalytic activity.
The synthesis of 5 multi-stage porous noble metal nano alloy/graphite alkene aeroge composite catalyst of embodiment
1, preparation method
The preparation method other conditions of the present embodiment catalyst with embodiment 1, the difference is that:
Cryogenic temperature is -196 DEG C, and cooling time is 0.1 h；Drying temperature is 0 DEG C, and dry vacuum degree is 20 Pa, drying time
For 12 h.
2, result
(1) the present embodiment obtains the metal nano alloy/graphite alkene composite aerogel of hierarchical porous structure, has three-dimensional continuous
Hierarchical porous structure, it is 1.08 cm3/g that mesoporous, which holds, and the aperture of macropore is about 55 μm, and mesoporous aperture is about 25 nm, ratio
Surface area is up to 400 m2/ g has cellular structure abundant, and the load capacity of porous noble metal nano alloy is up to 20
Wt% or more.
(3) the present embodiment obtains the metal nano alloy/graphite alkene composite aerogel of hierarchical porous structure, to be catalyzed formic acid point
For solution, unit mass and unit area catalytic activity are up to 560 mA/mg and 3.75 mA/cm respectively2, it is that commercial carbon carries
As many as nearly 6 times of platinum (20 wt%) catalyst, and keep extremely excellent electrochemical stability.
(4) the present embodiment obtains metal nano gold/graphene composite aerogel of hierarchical porous structure, more traditional three-dimensional
Graphene aerogel support type composite electro catalytic agent material shows lower overpotential and higher catalytic activity.
The preferred embodiment that the above specific embodiment is of the invention for ease of understanding and illustrates, but the invention is not limited to
Above-described embodiment does not mean that the present invention must rely on above-described embodiment and could implement.Person of ordinary skill in the field
It is the addition of equivalence replacement and auxiliary element to raw material selected by the present invention, specific it will be clearly understood that any improvement in the present invention
The selection etc. of mode, all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of preparation method of the efficient electric catalyst composite based on hierarchical porous structure graphene aerogel, feature exist
In, comprising the following steps:
S1. dispersion removing after graphite oxidation is obtained into evenly dispersed graphene oxide dispersion into solvent；Utilize oxidation
Agent performs etching pore-forming processing to graphene oxide dispersion, obtains surface with the graphite oxide abundant through meso-hole structure
Alkene lamella dispersion liquid；
S2. reducing agent is added and carries out reduction assembling, obtains the three-dimensional grapheme hydrogel with multi-stage artery structure；
S3. above-mentioned three-dimensional grapheme hydrogel is impregnated with metal front liquid solution to obtain using hydro-thermal method or high temperature pyrolytic cracking (HTP)
To the supported nano-gold category of hierarchical porous structure or the graphene composite hydrogel of nano metal alloy catalyst, freeze-drying is obtained
To the efficient electric catalyst composite.
2. preparation method according to claim 1, which is characterized in that in step S1, the graphene oxide dispersion
Lamellar spacing is 1~10 layer of carbon atom；The concentration of the graphene oxide dispersion is 0.1~20 mg/mL；Preferably, step
In S1, the quality and volume of the oxidant and graphene oxide dispersion are the mL of 0.1~10 g:1~100.
3. preparation method according to claim 1, which is characterized in that in step S2, the condition of the reduction assembling are as follows: 60
~90 DEG C of 0.5~6 h of reaction.
4. preparation method according to claim 1, which is characterized in that in step S3, in the metal front liquid solution before
The mass ratio for driving body and three-dimensional grapheme hydrogel is 1:20~1000.
5. preparation method according to claim 1, which is characterized in that in the efficient electric catalyst composite, nanometer
The type of metal or nano metal alloy is selected from Pt, Pd, Au, Ag, Ni, Fe, Co or Cu.
6. preparation method according to claim 1, which is characterized in that the condition of the high temperature pyrolysis reaction are as follows: 300~
500 DEG C of 3~8 h of reaction；Preferably, the condition of the hydro-thermal reaction are as follows: 160~200 DEG C of 3~24 h of reaction；Preferably, described
Solvent in step S1 be selected from water, acetone, ethyl alcohol, methanol, propyl alcohol, isopropanol, the tert-butyl alcohol, ethylene glycol, DMSO, DMF, THF or
One or more of pyridine；Preferably, the oxidant in the step S1 is selected from the potassium ferricyanide, iron chloride, hydrogen peroxide, Gao Meng
One or more of sour potassium or potassium chlorate；Preferably, the reducing agent in the step S2 is selected from sodium borohydride, hydroiodic acid, water
Close one or more of hydrazine, ascorbic acid, ammonium hydroxide or ethylenediamine.
7. claim 1~6 any one the method be prepared based on the efficient of hierarchical porous structure graphene aerogel
Elctro-catalyst composite material.
8. efficient electric catalyst composite according to claim 7, which is characterized in that the efficient elctro-catalyst is compound
Material has three-dimensional continuous hierarchical porous structure；1.08~1.85 cm3/g of Kong Rongwei；The aperture of macropore is 1~100 μm, is situated between
The aperture in hole is 2~50 nm；Specific surface area is 400~600 m2/g。
9. efficient electric catalyst composite described in claim 7 or 8 as or prepare application in electrode material.
10. a kind of catalyst carrier, which is characterized in that include efficient electric catalyst composite described in claim 7 or 8.
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