CN109300701B - Efficient electrocatalyst composite material and preparation method and application thereof - Google Patents
Efficient electrocatalyst composite material and preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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Abstract
The invention discloses a high-efficiency electrocatalyst composite material based on a hierarchical porous structure graphene aerogel and a preparation method and application thereof. The preparation method comprises the following steps: carrying out oxidation etching on the graphene oxide dispersion liquid to obtain graphene oxide lamellar dispersion liquid with abundant penetrating mesoporous structures on the surface; adding a reducing agent for reduction assembly to obtain the three-dimensional graphene hydrogel with the hierarchical pore structure; and (3) soaking the three-dimensional graphene hydrogel in a metal precursor solution, and performing freeze drying by using a hydrothermal method or a high-temperature pyrolysis method to obtain the high-efficiency electrocatalyst composite material. The special hierarchical pore structure fully exposes the catalytic active sites of the catalyst, greatly improves the wettability of the electrolyte to the active substances of the catalyst, and accelerates the mass transfer in the system in the catalytic process; in addition, the problem of electrocatalytic activity loss caused by electrochemical oxidation failure of the support material is avoided, and excellent catalytic activity, high catalytic stability and fast mass transfer characteristics are shown.
Description
Technical Field
The invention belongs to the technical field of nano material application and electrocatalyst synthesis and preparation. More particularly, relates to a high-efficiency electrocatalyst composite material based on a hierarchical porous structure graphene aerogel, and a preparation method and application thereof.
Background
Noble metals such as platinum (Pt), gold (Au), silver (Ag) and palladium (Pd) are one of the most widely used electrocatalyst materials at present, but the disadvantages of high cost, small reserves, poor stability and the like seriously limit the large-scale application of the noble metal electrocatalyst. To solve this problem, there are two general approaches: 1) the non-noble metal catalyst material with catalytic activity comparable to that of noble metal catalysts is developed, although the catalytic activity of the non-noble metal catalyst can be improved through structural design, the non-noble metal catalyst still has unsatisfactory catalytic activity and stability, and the potential of the non-noble metal catalyst for replacing the noble metal catalyst for large-scale application is greatly limited; 2) the nano-alloyed composite electrocatalyst is prepared based on the noble metal, and the active sites of the noble metal are fully exposed through precise structure control, so that the catalytic activity of the noble metal per unit mass is greatly improved, and the using amount of the noble metal catalyst is greatly reduced. Compared with the first scheme, the alloyed noble metal electrocatalyst material has higher electrochemical catalytic activity, lower overpotential and better stability, and has more excellent electrochemical catalytic comprehensive performance and wider application prospect.
Due to the agglomeration problem in the preparation process and the curing agglomeration and electrochemical corrosion leaching problems in the electrochemical process, the excellent comprehensive catalytic performance of the alloyed noble metal nano-alloy catalyst cannot be fully exerted in practical application. The introduction of the carbon carrier can well play a role in fully exposing, stabilizing and activating the catalytic active sites, and endows the final composite catalyst with better comprehensive catalytic performance. Graphene, as a highly graphitized two-dimensional carbon material, has excellent conductivity, stability and mechanical properties, as well as high carrier mobility and large specific surface area, and is an ideal catalyst support material from the structural and intrinsic characteristics. However, due to the nature of the two-dimensional material, when graphene is used as an electrocatalyst carrier, the graphene often faces a serious problem of stacking and agglomeration among sheets, which further causes problems of slow mass transfer rate and masked active sites.
The preparation of the graphene aerogel with the three-dimensional network structure through the self-assembly of the graphene sheet layers is an effective means for solving the problem of agglomeration which is easy to occur when the graphene sheet layers are used as carriers, and can provide a rapid channel for electron transmission. Moreover, because the inside mass transfer of traditional graphite alkene aerogel network often receives the limiting action of pore wall, can not be in the inside quick mass transfer process of forming of whole aerogel, compare with traditional graphite alkene aerogel, three-dimensional structure graphite alkene aerogel load type's noble metal nanometer alloy catalyst material's comprehensive electro-catalysis performance has very big promotion space in addition. At present, few reports exist on the obtained three-dimensional graphene-loaded nanoparticle composite material, and the nano alloy particles are difficult to be uniformly dispersed in the three-dimensional graphene structure, so that the catalytic activity is not ideal, and in addition, the support material is easy to lose the electrocatalytic activity due to electrochemical oxidation failure.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings of the prior art and provide a high-efficiency electrocatalyst composite material based on the graphene aerogel with the hierarchical pore structure, which has the advantages of fast mass transfer, high activity and high stability.
The first purpose of the invention is to provide a preparation method of a high-efficiency electrocatalyst composite material based on a hierarchical porous structure graphene aerogel.
A second object of the present invention is to provide a highly efficient electrocatalyst composite prepared using the above method.
The third purpose of the invention is to provide the application of the high-efficiency electrocatalyst composite material as an electrode material or in the preparation of the electrode material.
It is a fourth object of the present invention to provide a catalyst support comprising the above high efficiency electrocatalyst composite.
The above purpose of the invention is realized by the following technical scheme:
a preparation method of a high-efficiency electrocatalyst composite material based on a hierarchical porous structure graphene aerogel comprises the following steps:
s1, dispersing and stripping the oxidized graphite into a solvent to obtain uniformly dispersed graphene oxide dispersion liquid; etching and pore-forming the graphene oxide dispersion liquid by using an oxidant to obtain a graphene oxide lamellar dispersion liquid with a rich penetrating mesoporous structure on the surface;
s2, adding a reducing agent for reduction assembly to obtain the three-dimensional graphene hydrogel with the hierarchical pore structure;
and S3, soaking the three-dimensional graphene hydrogel in a metal precursor solution, obtaining the graphene composite hydrogel loaded with the nano metal or nano metal alloy catalyst and having a hierarchical pore structure by using a hydrothermal method or a high-temperature pyrolysis method, and freeze-drying to obtain the high-efficiency electrocatalyst composite material.
According to the invention, a multi-level porous structure graphene aerogel carrier with fast mass transfer and high activity is obtained by introducing a mesoporous structure design on a macroporous structure graphene aerogel framework; the porous nano metal or nano metal alloy composite catalyst is continuously loaded on the aerogel framework with the hierarchical porous structure, so that the catalyst nanoparticles are stably dispersed, the active sites are fully exposed, the rapid mass transfer in the system is ensured, meanwhile, the nonmetal nanoparticles are well protected, and the rapid attenuation of the electrochemical catalytic performance of the catalyst caused by corrosion and dissolution in the electrochemical curing process and the electrochemical process is fully avoided; finally, the hierarchical porous structure nano metal/graphene aerogel or nano metal alloy/graphene aerogel electrocatalyst composite material with fast mass transfer, high activity and high stability is obtained.
Preferably, in step S3, in order to continuously introduce porous nanometal or porous nanometal alloy particles into the three-dimensional skeleton of the graphene hydrogel, the three-dimensional graphene hydrogel obtained in step S2 is subjected to solvent replacement, and one or more organic solvents selected from DMSO, NMP, ethanol, DMF, ethylene glycol, and glycerol are subjected to solvent replacement according to a required metal synthesis system or metal alloy synthesis system, so as to obtain the target solvent-filled multi-level porous graphene hydrogel.
Preferably, in step S1, the graphene oxide dispersion liquid has a sheet thickness of 1 to 10 carbon atoms.
Preferably, the concentration of the graphene oxide dispersion liquid is 0.1-20 mg/mL.
More preferably, the concentration of the graphene oxide dispersion liquid is 2-10 mg/mL. For example, 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 mass volume of the oxidant and the graphene oxide dispersion liquid is 0.1-10 g: 1-100 mL. For example, 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 step S1 is selected from one or more of potassium ferricyanide, ferric chloride, hydrogen peroxide, potassium permanganate, and potassium chlorate.
Preferably, in step S1, the dispersion and exfoliation method is at least one selected from ball milling dispersion, mechanical stirring, ultrasonic dispersion, magnetic stirring, or high-pressure homogeneous dispersion and exfoliation methods.
Preferably, the solvent in step S1 is selected from one or more of water, acetone, ethanol, methanol, propanol, isopropanol, tert-butanol, ethylene glycol, DMSO, DMF, THF, or pyridine.
Preferably, in step S2, the conditions of the reductive assembly are: reacting for 0.5-6 h at 60-90 ℃.
More preferably, in step S2, the conditions for the reductive assembly are: reacting at 90 ℃ for 3 h.
Preferably, in step S2, the amount of the reducing agent added is 0.01% to 5% of the graphene oxide lamellar dispersion liquid.
More preferably, in step S2, the amount of the reducing agent added is 0.01% to 1% of the graphene oxide lamellar dispersion liquid.
Preferably, the reducing agent in step S2 is selected from one or more of sodium borohydride, hydroiodic acid, hydrazine hydrate, ascorbic acid, ammonia water, and ethylenediamine.
Preferably, in step S3, the mass ratio of the precursor in the metal precursor solution to the three-dimensional graphene hydrogel is 1: 20 to 1000. For example, 1: 20. 1: 50. 1: 100. 1: 200. 1: 300. 1: 450. 1: 500. 1: 600. 1: 900. 1: 1000, etc.
Preferably, the soaking time is 6-48 h. For example, 6 h, 10 h, 12 h, 15 h, 20 h, 24 h, 30 h, 36 h, 40 h, 48 h, etc.
Preferably, in the high-efficiency electrocatalyst composite, the type of the nano-metal or nano-metal alloy is selected from Pt, Pd, Au, Ag, Ni, Fe, Co, Cu, or the like. The type and the proportion can be matched at will, the particle size of the nano metal or the nano metal alloy is 3-15 nm, and the nano metal or the nano metal alloy is uniformly distributed on the framework of the graphene hydrogel. Meanwhile, the electrocatalyst composite material has the advantages of high specific surface area, rich pore channel structures, high electron transmission and mass transmission rate, prevention of agglomeration of graphene and nano particles, high loading amount of metal or metal alloy catalyst, excellent catalytic performance, lower overpotential (high energy efficiency) compared with the traditional three-dimensional graphene aerogel supported composite electrocatalyst material, and capability of selecting components of the catalyst according to different requirements.
Preferably, the metal precursor solution is selected from one or more of Pt, Pd, Au, Ag, Ni, Fe, Co and Cu; if the metal precursor solution is an alloy, the proportion of the metal precursor solution can be adjusted and controlled at will.
More preferably, the nano metal alloy is a nano platinum nickel metal alloy.
Preferably, the conditions of the pyrolysis reaction are as follows: reacting for 3-8 h at 300-500 ℃.
More preferably, the conditions of the pyrolysis reaction are: reacting for 4-6 h at 350-450 ℃.
Preferably, the conditions of the hydrothermal reaction are: reacting for 3-24 h at 160-200 ℃.
More preferably, the hydrothermal reaction conditions are: reacting for 6-12 h at 170-190 ℃.
The freeze drying is directional freeze drying or non-directional freeze drying, the freezing temperature is-196 ℃ to-5 ℃, and the freezing time is 0.1-10 h; the drying temperature is 0-15 ℃, the drying vacuum degree is 1-20 Pa, and the drying time is 12-72 h.
The efficient electrocatalyst composite material based on the graphene aerogel with the hierarchical porous structure prepared by the method is also within the protection scope of the invention.
The electrocatalyst composite material disclosed by the invention is complex in morphology, the obtained hierarchical porous structure precious metal nanoparticle gold/graphene aerogel electrocatalyst composite material is high in specific surface area and rich in pore channel structures, and the loading amount of a precious metal catalyst is up to more than 20 wt%. Taking the catalytic formic acid decomposition as an example, the catalytic activity of the catalyst per unit mass and unit area is respectively as high as 650 mA/mg and 4.55 mA/cm2And the composite electrocatalyst material has lower overpotential (high energy efficiency) compared with the traditional three-dimensional graphene aerogel supported composite electrocatalyst material.
The high-efficiency electrocatalyst composite material has a three-dimensional continuous hierarchical pore structure; carrying out dry distillation on the obtained product according to the hole volume of 1.08-1.85 cm; the aperture of the macropores is 1-100 mu m, and the aperture of the mesopores is 2-50 nm; the specific surface area is 400-600 m2/g。
When the specific surface area of the high-efficiency electrocatalyst composite material is 400 m2At/g, the catalyst loading is at least 20 wt%.
The high-efficiency electrocatalyst composite material can be used as an electrode material to be applied to the manufacture of lithium ion batteries, super capacitors and the like. Accordingly, the application of the high-efficiency electrocatalyst composite material as or in the preparation of an electrode material is also within the protection scope of the invention.
The invention also provides a catalyst carrier containing the high-efficiency electrocatalyst composite material, which has better stability and excellent catalytic activity.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, a large number of through mesoporous structures are introduced on the graphene aerogel framework, so that the problem of slow mass transfer inside the catalyst material caused by the blocking effect of the pore wall of the traditional three-dimensional graphene aerogel is well solved.
(2) According to the invention, the graphene aerogel with the hierarchical pore structure is combined with the nano metal or nano metal alloy with the porous structure, so that the electrocatalyst composite material with the hierarchical pore structure is effectively formed, the active sites of the catalyst are fully exposed, the catalytic activity of the catalyst is greatly improved, and the mass transfer in the system in the catalytic process is accelerated; in addition, in the compounding process, compared with the composite material obtained by a common solution blending method, the simple and feasible hydrothermal in-situ growth method is adopted, the porous nano metal or nano metal alloy is dispersed more uniformly, the binding force between the porous nano metal or nano metal alloy and the multi-level pore structure graphene aerogel framework is stronger, the falling and curing in the long-term recycling process are avoided, and the stability of the catalyst is further improved.
(3) The hierarchical porous graphene aerogel framework with high graphitization degree can be used as an excellent support material in an electrocatalysis process, so that the problem of electrocatalysis activity loss caused by electrochemical oxidation failure of the support material is avoided; the catalyst is used in electrocatalytic reaction, such as formic acid oxidation, and simultaneously shows excellent catalytic activity, high catalytic stability and fast mass transfer characteristic.
(4) The method has the advantages of simple reaction process, few reaction steps, short reaction period, good repeatability and the like, and has good application prospect and wide development space in the field of electrocatalysts.
Drawings
FIG. 1 is a transmission electron microscope image of a porous graphene oxide sheet layer of the present invention.
Fig. 2 is a digital photograph of the multi-level pore graphene hydrogel of the present invention.
Fig. 3 is a transmission electron microscope and a scanning electron microscope picture of the hierarchical porous noble metal nano alloy/graphene aerogel composite catalyst obtained by the present invention.
Fig. 4 is a nitrogen DFT pore size distribution diagram of the multi-level pore noble metal nano-alloy/graphene aerogel composite catalyst obtained by the present invention.
Fig. 5 is a formic acid catalysis performance diagram of the hierarchical porous noble metal nano alloy/graphene aerogel composite catalyst prepared by the present invention.
Fig. 6 is an ampere-hour curve of the hierarchical porous noble metal nano-alloy/graphene aerogel composite catalyst prepared according to the present invention.
Fig. 7 is a comparison graph of catalytic performance of formic acid between the hierarchical porous noble metal nano alloy/graphene aerogel composite catalyst prepared according to the present invention and the conventional graphene aerogel supported porous noble metal nano alloy composite catalyst.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1 Synthesis of hierarchical porous noble Metal Nanoalloy/graphene aerogel composite catalyst
1. The preparation method of the hierarchical porous noble metal porous nano alloy/graphene aerogel composite catalyst comprises the following steps:
(1) synthesizing graphene oxide lamellar dispersion liquid with rich mesoporous structures on the surface:
synthesizing a graphene oxide dispersion liquid: dispersing 5 g of natural crystalline flake graphite, 5 g of sodium nitrate and 15 g of potassium permanganate in 150 mL of concentrated sulfuric acid, stirring for reaction for 10 hours, heating to 95 ℃ for reaction for 0.5 hour, standing, pouring out supernatant, centrifugally washing the precipitate for several times until the precipitate is neutral, and stripping the precipitate into solvent water through ultrasonic dispersion for 15 min to obtain uniformly dispersed graphene oxide dispersion liquid;
etching and pore-forming treatment: taking 100 mL of 5 mg/mL graphene oxide solution, adding 2.5 g of ferric chloride serving as an oxidant, boiling for 3 h for etching and pore-forming, and centrifugally washing for 2-4 times to obtain graphene oxide lamellar dispersion liquid with a rich mesoporous structure on the surface;
(2) synthesizing the three-dimensional graphene hydrogel with the hierarchical pore structure:
taking 100 mL of graphene oxide lamellar dispersion liquid with a surface having a rich mesoporous structure of 3 mg/mL, adding 3 mL of hydriodic acid (the addition amount of the hydriodic acid is 3% of the graphene oxide lamellar dispersion liquid), and reacting at 90 ℃ for 3 hours to obtain the three-dimensional graphene hydrogel with the multistage pore structure;
(3) synthesizing a hierarchical porous noble metal porous nano alloy/graphene aerogel composite catalyst:
soaking and washing the three-dimensional graphene hydrogel with a large amount of clear water, and then placing the three-dimensional graphene hydrogel in a mixed solution of chloroplatinic acid and nickel chloride, selecting ethanol for solvent replacement for 6 hours, wherein the mass ratio of a precursor in a metal precursor solution (the mixed solution of chloroplatinic acid and nickel chloride) to the three-dimensional hydrogel is 1: 20;
and after the replacement is finished, the whole body is transferred into a hydrothermal kettle, the temperature is raised to 170 ℃ for reaction for 6 hours, and finally, the multilevel porous noble metal nano alloy/graphene aerogel composite catalyst (namely the nano platinum nickel metal alloy/graphene aerogel composite catalyst) can be obtained through washing and freeze drying (wherein the freezing temperature is-5 ℃, the freezing time is 10 hours, the drying temperature is 15 ℃, the drying vacuum degree is 1 Pa, and the drying time is 72 hours).
2. Preparation of traditional noble metal nano alloy/graphene aerogel composite catalyst
In order to compare the performances, the preparation method of the traditional graphene aerogel supported porous nano metal alloy composite catalyst material is basically the same as that of the multi-stage porous noble metal porous nano alloy/graphene aerogel composite catalyst, except that the graphene oxide lamella is not subjected to etching pore-forming treatment, namely, the steps of adding ferric chloride and boiling are not carried out.
3. Results
(1) In this example, a porous graphene oxide sheet layer (as shown in fig. 1) is obtained by oxidation etching, and a multi-level porous graphene hydrogel (as shown in fig. 2) is obtained by adding hydroiodic acid at 90 ℃ and reacting for 3 h.
(2) In this embodiment, a transmission electron microscope image of the obtained metal nano alloy/graphene composite aerogel with a hierarchical pore structure is shown in fig. 3, and the obtained metal nano alloy/graphene composite aerogel has a three-dimensional continuous hierarchical pore structure, wherein a pore volume is 1.85 cm high year/g, a pore diameter of a large pore is about 50 μm, and a pore diameter of a mesoporous pore is about 20 nm; the specific surface area is as high as 517.4 m2The alloy has rich pore canal structure and the loading amount of the porous noble metal nano alloy is more than 20 wt percent (shown in figure 4).
(3) The true bookIn the embodiment, the metal nano alloy/graphene composite aerogel with the hierarchical pore structure is obtained, the catalytic activity of the metal nano alloy/graphene composite aerogel in unit mass and unit area is up to 580 mA/mg and 4.0 mA/cm respectively by taking catalytic formic acid decomposition as an example2(as shown in fig. 4), 6 times as much as the commercial platinum on carbon (20 wt%) catalyst, and maintains very excellent electrochemical stability (as shown in fig. 6).
(4) In this embodiment, the metal nano-alloy/graphene composite aerogel (multi-level porous noble metal nano-alloy/graphene aerogel composite catalyst) with a multi-level porous structure shows a lower overpotential and a higher catalytic activity than a conventional three-dimensional graphene aerogel supported composite electrocatalyst material (conventional noble metal nano-alloy/graphene aerogel composite catalyst) (as shown in fig. 7).
Example 2 Synthesis of hierarchical porous noble Metal Nanoalloy/graphene aerogel composite catalyst
1. Preparation method
The catalyst of this example was prepared under otherwise the same conditions as in example 1, except that:
(1) the reducing agent is sodium borohydride;
(2) the conditions of the hydrothermal reaction are as follows: carrying out hydrothermal reaction for 6 h at 180 ℃.
2. Results
(1) The metal nanoparticle alloy/graphene composite aerogel with the hierarchical pore structure is obtained by the embodiment, and the specific surface area of the metal nanoparticle alloy/graphene composite aerogel is as high as 510 m2The alloy has rich pore canal structure, and the loading amount of the porous noble metal nano alloy is up to more than 20 wt%.
(3) In this example, the metal nano-alloy/graphene composite aerogel with a hierarchical pore structure is obtained, taking catalytic formic acid decomposition as an example, the catalytic activities per unit mass and unit area of the metal nano-alloy/graphene composite aerogel are respectively as high as 520 mA/mg and 3.55 mA/cm2Nearly 6 times as much as commercial platinum on carbon (20 wt%) catalysts and maintains extremely excellent electrochemical stability.
(4) The metal nanoparticle gold/graphene composite aerogel with the hierarchical pore structure obtained by the embodiment shows lower overpotential and higher catalytic activity than the traditional three-dimensional graphene aerogel supported composite electrocatalyst material.
Example 3 Synthesis of hierarchical porous noble Metal Nanoalloy/graphene aerogel composite catalysts
1. Preparation method
The catalyst of this example was prepared under otherwise the same conditions as in example 2, except that:
(1) the reducing agent is ascorbic acid;
(2) the conditions of the hydrothermal reaction are as follows: carrying out hydrothermal reaction at 180 ℃ for 12 h.
2. Results
(1) The metal nanoparticle alloy/graphene composite aerogel with the hierarchical pore structure is obtained by the embodiment, and the specific surface area of the metal nanoparticle alloy/graphene composite aerogel is up to 450 m2The alloy has rich pore canal structure, and the loading amount of the porous noble metal nano alloy is up to more than 20 wt%.
(3) In this example, the metal nano-alloy/graphene composite aerogel with a hierarchical pore structure is obtained, taking catalytic formic acid decomposition as an example, the catalytic activities per unit mass and unit area of the metal nano-alloy/graphene composite aerogel are as high as 510 mA/mg and 3.55 mA/cm, respectively25 times as much as commercial platinum on carbon (20 wt%) catalyst and maintains extremely excellent electrochemical stability.
(4) The metal nanoparticle gold/graphene composite aerogel with the hierarchical pore structure obtained by the embodiment shows lower overpotential and higher catalytic activity than the traditional three-dimensional graphene aerogel supported composite electrocatalyst material.
Example 4 Synthesis of hierarchical porous noble Metal Nanoalloy/graphene aerogel composite catalysts
1. Preparation method
The catalyst of this example was prepared under otherwise the same conditions as in example 2, except that:
after the replacement is completed, the multilevel pore structure graphene hydrogel with the metal precursor solution is directly freeze-dried, then the obtained composite aerogel is subjected to high-temperature treatment at 500 ℃ for 3 hours under the argon protection condition, and a high-temperature pyrolysis method is utilized to prepare the multilevel pore nano metal/graphene aerogel composite catalyst.
2. Results
(1) The metal nanoparticle alloy/graphene composite aerogel with the hierarchical pore structure is obtained by the embodiment, and the specific surface area of the metal nanoparticle alloy/graphene composite aerogel is up to 405 m2The alloy has rich pore canal structure, and the loading amount of the porous noble metal nano alloy is up to more than 20 wt%.
(3) In this example, the metal nano-alloy/graphene composite aerogel with a hierarchical pore structure is obtained, taking catalytic formic acid decomposition as an example, the catalytic activities per unit mass and unit area of the metal nano-alloy/graphene composite aerogel are respectively as high as 555 mA/mg and 3.7 mA/cm2Nearly 6 times as much as commercial platinum on carbon (20 wt%) catalysts and maintains extremely excellent electrochemical stability.
(4) The metal nanoparticle gold/graphene composite aerogel with the hierarchical pore structure obtained by the embodiment shows lower overpotential and higher catalytic activity than the traditional three-dimensional graphene aerogel supported composite electrocatalyst material.
Example 5 Synthesis of hierarchical porous noble Metal Nanoalloy/graphene aerogel composite catalysts
1. Preparation method
The catalyst of this example was prepared under otherwise the same conditions as in example 1, except that:
the freezing temperature is-196 ℃, and the freezing time is 0.1 h; the drying temperature is 0 ℃, the drying vacuum degree is 20 Pa, and the drying time is 12 h.
2. Results
(1) In this embodiment, the metal nanoparticle alloy/graphene composite aerogel with the hierarchical pore structure has a three-dimensional continuous hierarchical pore structure, wherein the pore volume is 1.08 cm for each gram, the pore diameter of a large pore is about 55 μm, the pore diameter of a mesoporous pore is about 25 nm, and the specific surface area is as high as 400 m2The alloy has rich pore canal structure, and the loading amount of the porous noble metal nano alloy is up to more than 20 wt%.
(3) In this example, the metal nano-alloy/graphene composite aerogel with a hierarchical pore structure is obtained, taking catalytic formic acid decomposition as an example, the catalytic activities per unit mass and unit area of the metal nano-alloy/graphene composite aerogel are respectively as high as 560 mA/mg and 3.75 mA/cm2Is commercial platinum on carbon(20 wt%) nearly 6 times as much as the catalyst and maintains extremely excellent electrochemical stability.
(4) The metal nanoparticle gold/graphene composite aerogel with the hierarchical pore structure obtained by the embodiment shows lower overpotential and higher catalytic activity than the traditional three-dimensional graphene aerogel supported composite electrocatalyst material.
The above detailed description is of the preferred embodiment for the convenience of understanding the present invention, but the present invention is not limited to the above embodiment, that is, it is not intended that the present invention necessarily depends on the above embodiment for implementation. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (10)
1. A preparation method of a high-efficiency electrocatalyst composite material based on a hierarchical porous structure graphene aerogel is characterized by comprising the following steps:
s1, dispersing and stripping the oxidized graphite into a solvent to obtain uniformly dispersed graphene oxide dispersion liquid; etching and pore-forming the graphene oxide dispersion liquid by using an oxidant to obtain a graphene oxide lamellar dispersion liquid with a rich penetrating mesoporous structure on the surface;
s2, adding a reducing agent for reduction assembly to obtain the three-dimensional graphene hydrogel with the hierarchical pore structure;
s3, soaking the three-dimensional graphene hydrogel in a metal precursor solution, obtaining the graphene composite hydrogel loaded with the nano metal or nano metal alloy catalyst and having a multi-stage pore structure by using a hydrothermal method, and freeze-drying to obtain the high-efficiency electrocatalyst composite material; or soaking the three-dimensional graphene hydrogel in a metal precursor solution, freeze-drying, and then obtaining the high-efficiency electrocatalyst composite material by using a high-temperature pyrolysis method under the protection of inert gas;
in the step S1, the thickness of a lamella of the graphene oxide dispersion liquid is 1-10 layers of carbon atoms; the concentration of the graphene oxide dispersion liquid is 0.1-20 mg/mL;
in step S2, the conditions for the reductive assembly are: reacting for 0.5-6 h at 60-90 ℃;
in step S3, the mass ratio of the precursor in the metal precursor solution to the three-dimensional graphene hydrogel is 1: 20-1000 parts;
in the high-efficiency electrocatalyst composite material, the type of the nano metal or the nano metal alloy is selected from Pt, Pd, Au, Ag, Ni, Fe, Co or Cu;
the conditions of the high-temperature pyrolysis reaction are as follows: reacting for 3-8 h at 300-500 ℃.
2. The preparation method according to claim 1, wherein in step S1, the mass and volume of the oxidant and graphene oxide dispersion liquid are 0.1-10 g: 1-100 mL.
3. The preparation method according to claim 1, wherein the hydrothermal reaction conditions are: reacting for 3-24 h at 160-200 ℃.
4. The method according to claim 1, wherein the solvent in step S1 is selected from one or more of water, acetone, ethanol, methanol, propanol, isopropanol, tert-butanol, ethylene glycol, DMSO, DMF, THF and pyridine.
5. The preparation method according to claim 1, wherein the oxidant in step S1 is one or more selected from potassium ferricyanide, ferric chloride, hydrogen peroxide, potassium permanganate, and potassium chlorate.
6. The method according to claim 1, wherein the reducing agent in step S2 is selected from one or more of sodium borohydride, hydroiodic acid, hydrazine hydrate, ascorbic acid, ammonia water, and ethylenediamine.
7. The high-efficiency electrocatalyst composite material based on the graphene aerogel with the hierarchical pore structure, prepared by the method of any one of claims 1 to 6.
8. The high efficiency electrocatalyst composite according to claim 7, wherein the high efficiency electrocatalyst composite has a three-dimensional continuous hierarchical pore structure; carrying out dry distillation on the obtained product according to the hole volume of 1.08-1.85 cm; the aperture of the macropores is 1-100 mu m, and the aperture of the mesopores is 2-50 nm; the specific surface area is 400-600 m 2/g.
9. Use of the high efficiency electrocatalyst composite according to claim 7 or 8 as or in the preparation of an electrode material.
10. A catalyst support comprising the high efficiency electrocatalyst composite according to claim 7 or 8.
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| CN110860287B (en) * | 2019-11-07 | 2022-08-19 | 湖北工业大学 | Preparation method of graphene/copper nanocrystalline composite catalytic material |
| CN111250073A (en) * | 2020-02-18 | 2020-06-09 | 北京科技大学 | Preparation method of graphene electrocatalyst with hierarchical pore channel three-dimensional structure |
| CN111847430A (en) * | 2020-07-15 | 2020-10-30 | 广东墨睿科技有限公司 | Preparation method of high-strength high-resilience graphene aerogel |
| CN111992149A (en) * | 2020-08-12 | 2020-11-27 | 中山大学 | Preparation method of porous carrier supported metal aerogel composite material |
| CN113235130B (en) * | 2021-04-12 | 2022-09-06 | 中山大学 | Low-platinum composite material based on tungsten oxide/graphene aerogel and preparation method and application thereof |
| CN113718281B (en) * | 2021-09-26 | 2023-01-13 | 北京三川烯能科技有限公司 | Graphene quantum dot/MXene nanosheet two-dimensional composite material and preparation method and application thereof |
| CN114182286A (en) * | 2021-11-29 | 2022-03-15 | 太原理工大学 | Preparation of Ni-Ti by hydrothermal method3C2Method for compounding electrocatalysts |
| CN116062738B (en) * | 2022-12-30 | 2024-06-11 | 中国科学院福建物质结构研究所 | Secondary reinforced graphene aerogel and preparation method and application thereof |
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