CN111715259B - Preparation method of reduced graphene oxide loaded iron-based nanoparticle composite electrocatalytic material - Google Patents
Preparation method of reduced graphene oxide loaded iron-based nanoparticle composite electrocatalytic material Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 132
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 94
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 65
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- 239000000463 material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
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- 239000002253 acid Substances 0.000 claims abstract description 5
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- -1 nitrogen-containing compound Chemical class 0.000 claims description 3
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- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 2
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- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- SPKJCVZOZISLEI-UHFFFAOYSA-N cyclopenta-1,3-diene;1-cyclopenta-1,3-dien-1-ylethanone;iron(2+) Chemical compound [Fe+2].C=1C=C[CH-]C=1.CC(=O)C1=CC=C[CH-]1 SPKJCVZOZISLEI-UHFFFAOYSA-N 0.000 description 1
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- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- B01J35/393—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/33—
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- B01J35/615—
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- B01J35/638—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a preparation method of a reduced graphene oxide loaded iron-based nanoparticle composite electrocatalytic material, belonging to the field of electrochemical energy catalysis and comprising the following steps of: preparing an iron/nitrogen precursor, synchronously decomposing and fumigating to prepare a composite material precursor, cleaning the composite material precursor in strong acid or strong alkali, removing non-catalytic active substances, and freeze-drying to obtain the composite material. The method simplifies the process flow, realizes synchronous pyrolysis of the iron-based precursor, reduction and nitrogen doping of the graphene oxide, and is suitable for large-scale preparation of the graphene-loaded nano iron-based compound composite electrocatalytic material; and has excellent properties: the particle size of the nano iron-based compound is less than 5nm, and the specific surface area is more than 300m 2 Per g, pore volume greater than 1.5cm 3 And/g, in the 0.1M KOH electrolyte saturated with oxygen, the electrocatalytic oxygen reduction initial potential is more than 0.9V (vs. RHE), and the half-wave potential is 8.3V (vs. RHE).
Description
Technical Field
The invention belongs to the field of electrochemical energy catalysis, and particularly relates to a preparation method of a reduced graphene oxide loaded iron-based nanoparticle composite electrocatalytic material and the electrocatalytic material.
Background
Energy problems and environmental problems are major problems in the development of the world today. With the social development, the problems of fossil energy crisis and environmental pollution become more serious, and the development of pollution-free and sustainable energy has become a research hotspot in the field of current energy and environment. Among them, electrochemical energy conversion has received extensive attention from researchers in recent years, and the development of a high-activity, low-cost, stable electrocatalyst is a great challenge in the field of electrochemical energy conversion at present.
The fuel cell has a series of advantages of high energy conversion rate, environmental friendliness, high operational reliability and the like, and is considered to be the most promising energy conversion device. The cathode of a fuel cell, such as a fuel cell, metal-air battery, typically performs electrochemical energy conversion by the Oxygen Reduction Reaction (ORR). However, the ORR reaction is complex, involving the transfer of 4 protons to 4 electrons, and its kinetics is slow, thus requiring a catalyst to lower the reaction energy barrier and improve the electrocatalytic reaction kinetics. Most of the current commercial ORR electrocatalysts are platinum nanoparticles supported by carbon-based materials, but the large-scale commercialization of fuel cells is severely limited due to the reasons of resource scarcity, high price, easy poisoning and deactivation and the like. Therefore, researchers have desired to develop a catalyst having low price, good stability and high activity instead of the Pt-based catalyst. In recent years, it has been reported that Pt is replaced by a catalyst obtained by doping Pt with Pd or using Pd as a main component. However, the price of Pd has greatly increased since 2018, the price of Pd is far higher than that of Pt at present, and the cost advantage is reversed. Therefore, the actual idea of the catalyst cost reduction should be to find binary or multi-element alloy catalysts containing Fe, co, ni, and other really inexpensive transition metals as main components.
Researches show that the Pt-based catalytic performance is greatly reduced along with the increase of reaction temperature and the lengthening of reaction time, and the main reason is the migration and agglomeration of nano-particles on the surface of a carrier. Therefore, it is critical to select a more suitable catalyst support to avoid performance degradation. Since the advent of graphene, graphene is considered to be an ideal catalyst carrier due to its excellent properties such as high conductivity, large specific surface area, surface modification, and the like. But intrinsic carbon to O 2- And ORR intermediates (-OH, -OOH, etc.) are inert, so how sp will be adsorbed 2 Carbon conversion to ORR active electrocatalyst is the focus of research on carbon-based electrocatalysts.
In recent years, the realization of high catalytic performance by regulating defects of graphene-based materials is receiving more and more attention, the traditional defects mostly mean that unsaturated sites such as edges, vacancies, steps and the like of graphene can be used as catalytic active sites, and at present, catalyst research is deeply conducted on how to construct new catalytic active sites by utilizing the characteristics of difference, deviation, deletion and the like of electron distribution, such as single atom insertion, topological structure formation, co-doping and other modification modes. The carbon-based material has n/p type semiconductor characteristics through doping of heteroatoms (metal and nonmetal elements), and an electron cloud structure of graphene is changed. More recently, it has been discovered that the electronic and chemical properties of the surface of the graphene nanosheet layer can be effectively improved by doping with heteroatoms (such as nitrogen, phosphorus, sulfur, boron, etc.). Due to the difference of electronegativity, atomic size and binding state, the electron spin and charge distribution can be refined by doping, the hydrophilicity/hydrophobicity of the carbon material is improved, and good electrocatalysis performance is realized. In addition, the carbon-based material modified by the defects is also beneficial to anchoring of metal nanoparticles, reduces migration and agglomeration on the surface, and further improves catalytic activity and stability.
Although great progress has been made in loading nano metal compounds on graphene, the preparation method includes hydrothermal method, pyrolysis method, hydrothermal reaction method and the like. However, these in situ synthesis methods are limited by the uneven concentration of the reducing agent solution or the uneven mixing degree of the precursor and the graphene-based material, and the prepared metal nanomaterial is generally large in size, and has a weak binding force with the graphene substrate, so that the surface migration and agglomeration of the metal nanomaterial in a long-term cycle process cannot be prevented.
Disclosure of Invention
The invention aims to: aiming at the problem that the general technology cannot synchronously realize the large-scale doping of the graphene-based material and the loading of the nano iron-based metal compound with the size less than 5nm, the invention provides a preparation method of the reduced graphene oxide loaded iron-based nano particle composite electrocatalytic material.
The technical scheme adopted by the invention is as follows:
a preparation method of a reduced graphene oxide loaded iron-based nanoparticle composite electrocatalytic material comprises the following steps:
step 1: preparing an iron/nitrogen precursor: ferrocene or ferrocene derivatives and nitrogen-containing compounds are mixed according to the mass ratio of 1: (3-5) fully grinding and uniformly mixing to obtain an iron/nitrogen precursor mixture;
step 2: synchronously decomposing and fumigating to prepare a composite material precursor: placing the prepared graphene oxide aerogel on the upper layer of a fumigation reaction vessel, placing an iron/nitrogen precursor on the lower layer of the fumigation reaction vessel, placing the fumigation reaction vessel in a high-temperature atmosphere furnace under the protection of inert gas, introducing the inert gas to form an inert atmosphere, heating to 400-1000 ℃ at the speed of 5-10 ℃/min, preserving heat for 2-6h, and then cooling to room temperature in the inert gas atmosphere to obtain a composite material precursor;
and 3, step 3: and (3) cleaning the composite material precursor in strong acid or strong alkali, removing non-catalytic active substances, and freeze-drying to obtain the graphene-loaded nano iron-based composite electrocatalytic composite material. Wherein the non-catalytic active substances such as iron simple substance, amorphous ferric oxide, participated soluble ammonium salt, ferric salt and the like are useless or harmful substances for subsequent electrocatalytic performance.
According to the invention, a fumigation method is adopted, and a gaseous nitrogen-containing and iron-containing atmosphere formed by decomposing an iron/nitrogen precursor at a high temperature is utilized to uniformly load the nano iron-based compound with the size of less than 5 nanometers on the surface of the graphene substrate, so that the prepared graphene-loaded nano iron-based compound composite material has high catalytic activity and high specific surface area.
Preferably, the ferrocene derivatives have melting point higher than 120 ℃ and decomposition temperature higher than 180 ℃, and comprise any one or more of ferrocene derivatives containing acyl, amide and acylhydrazone groups; the nitrogen-containing compound comprises one or more of urea, melamine, polyaniline, p-phenylenediamine and 8-hydroxyquinoline.
Preferably, the addition amount of the graphene oxide aerogel accounts for 30-40% of the total mass of the iron/nitrogen precursor and the graphene oxide aerogel.
Preferably, after the fumigation reaction vessel is placed in a high-temperature atmosphere furnace, inert gas is introduced for 25-35min at a gas flow rate of 180-220sccm to form an inert atmosphere; then reducing the flow of the inert gas to 20-80sccm and continuing to introduce the inert gas.
Preferably, the preparation method of the graphene oxide aerogel in the step 2 comprises the following steps: firstly, washing graphite oxide by using a nonpolar solvent A, wherein the weight ratio of the graphite oxide to the solvent A is: polar solvent B = (5-8): (92-95), further dissociating the cleaned graphite oxide in a polar solvent B to obtain brown or chestnut gel graphene oxide, and freeze-drying at-40-60 ℃ for 24-48h in an inert gas atmosphere to obtain the graphene oxide with the surface area of 100-150m 2 Per g, pore volume of 0.5-1.0cm 3 And the viscosity of the graphene oxide aerogel is 300-650mPa & s.
Preferably, the weight ratio of O/C in the graphite oxide is 1 to 1.7, preferably 1.5 to 1.7; the graphite oxide synthesis method can be a Hummers method, a modified Hummers method, a Brodie method or a Staudenmaier method, and aims to obtain the graphene oxide gel by subsequent automatic stripping by controlling the O/C ratio.
Preferably, the nonpolar solvent A is any one or more of diethyl ether, petroleum ether, tetrahydrofuran and ethanol with the polarity not more than 5.0; aims to reduce the stripping of graphite oxide, and inert gas is selected to isolate oxygen in the air in the cleaning process.
Preferably, the polar solvent B is any one or more of deionized water with polarity greater than 8, N-dimethylformamide and methylacetamide. Deionized water is preferably used as the stripping substance in the invention, and the deionized water also needs to be subjected to oxygen removal treatment.
Preferably, the strong acid or strong base in step 3 is 0.1M KOH or 0.1M HClO 4 Or 0.5M H 2 SO 4 And (3) solution.
Preferably, the fumigation reaction vessel is a cylindrical container made of mullite, graphite, corundum and silicon carbide, and is divided into an upper layer and a lower layer which are communicated through a support arranged in the middle.
The reduced graphene oxide loaded iron-based nanoparticle composite electrocatalytic material is characterized in that reduced graphene oxide loaded iron-based nanoparticles comprise nano iron oxide, iron carbide and iron nitrideThe grain sizes of the iron oxide and the iron nitride are both 2-6nm, and the specific surface area is more than 350m 2 Per g, pore volume greater than 1.50cm 3 Per g, the weight content of Fe is 7-10%, the weight content of N is 5-7%, and the weight content of O is 15-19%.
Compared with the prior art, the invention has the beneficial effects that:
(1) In the obtained graphene-loaded nano iron-based compound composite material, the particle size of the nano iron-based compound is less than 5nm, and the specific surface area is more than 300m 2 Per g, pore volume greater than 1.5cm 3 (iv)/g, the oxygen reduction peak potential in the oxygen-saturated 0.1M KOH electrolyte is 0.830V (vs. RHE) or more, the half-wave potential is 0.780V (vs. RHE) or more, and after circulation for 10000 times, the oxygen reduction peak potential is 0.820V (vs. RHE) or more, and the half-wave potential is 0.770V (vs. RHE) or more, and the electrolyte has excellent performance.
(2) The method simplifies the process flow, realizes synchronous pyrolysis of the iron-based precursor, reduction and nitrogen doping of the graphene oxide, and is suitable for large-scale preparation of the graphene-loaded nano iron-based compound composite electrocatalytic material.
Drawings
FIG. 1 is a schematic view of a steamer vessel;
fig. 2 is an SEM image of the graphene oxide aerogel of example 1;
FIG. 3 is graphene oxide aerogel N of example 1 2 Adsorption and desorption curves;
FIG. 4 is a graph of pore volume versus pore diameter for the graphene oxide aerogel of example 1;
fig. 5 is an XRD spectrum of the reduced graphene oxide-supported iron-based nanoparticles of example 1;
fig. 6 is a particle size distribution diagram of reduced graphene oxide-supported iron-based nanoparticles of example 1;
FIG. 7 shows reduced graphene oxide loaded iron-based nanoparticles N of example 1 2 Adsorption and desorption curves;
FIG. 8 is a graph of pore volume versus pore diameter for reduced graphene oxide loaded iron-based nanoparticles of example 1;
fig. 9 is a position point diagram of EDS elemental analysis of reduced graphene oxide-supported iron-based nanoparticles of example 1;
FIG. 10 shows the reduced graphene oxide loaded iron-based nanoparticles of example 1 in oxygen saturated 0.1M KOH
CV curve in electrolyte;
fig. 11 is an SEM image of the graphene oxide aerogel of example 2;
FIG. 12 is the graphene oxide aerogel N of example 2 2 Adsorption and desorption curves;
FIG. 13 is a graph of the relationship between pore volume and pore diameter for graphene oxide aerogel of example 2;
fig. 14 is an XRD spectrum of the reduced graphene oxide-supported iron-based nanoparticles of example 2;
fig. 15 is a particle size distribution diagram of reduced graphene oxide-supported iron-based nanoparticles of example 2;
FIG. 16 shows reduced graphene oxide loaded iron-based nanoparticles N of example 2 2 Adsorption and desorption curves;
fig. 17 is a graph of pore volume versus pore diameter for reduced graphene oxide loaded iron-based nanoparticles of example 2;
fig. 18 is a CV curve of the reduced graphene oxide-supported iron-based nanoparticles of example 2 in an oxygen-saturated 0.1M KOH electrolyte.
Labeled as: 1-fumigating utensil, 2-upper layer, 3-lower layer and 4-support.
Detailed Description
The present invention will be described in further detail in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
According to the invention, a fumigation method is adopted, and a gaseous nitrogen-containing and iron-containing atmosphere formed by decomposing an iron/nitrogen precursor at a high temperature is utilized to uniformly load the nano iron-based compound with the size of less than 5 nanometers on the surface of the graphene substrate, so that the prepared graphene-loaded nano iron-based compound composite material has high catalytic activity and high specific surface area.
Example 1
A preparation method of a graphene-loaded nano iron-based composite electro-catalytic material comprises the following steps:
the method comprises the following steps: 10g of brown graphite oxide prepared by a commercial improved Hummers method (the graphite oxide is stored in a dark vacuum environment, the using time does not exceed 30 days of the production date), and then high-purity nitrogen (99.95%) is introduced into 250 ml of absolute ethyl alcohol for 30min to realize the oxygen removal treatment in the ethyl alcohol; and then carrying out centrifugal cleaning on the graphite oxide for 3-5 times to obtain the cleaned graphite oxide.
Step two: taking 190 ml of de-ionized water (the conductivity is 0.055 mu S/cm) after deoxygenation, adding graphite oxide into the de-ionized water under the condition of high-speed stirring (1500 rad/min), and stirring at high speed for 1h to obtain brown hydrogel-like graphene oxide paste;
step three: placing the graphene oxide paste in a 100 x 150 x 25mm enamel tray, wherein the liquid level height is 18 mm, placing the graphene oxide paste in a low-temperature freeze-dried phase body, closing the sealing, firstly vacuumizing, introducing high-purity nitrogen from an air inlet after the vacuum degree reaches 0.01 MPa, vacuumizing again, repeating the steps for 3 times, then starting a low-temperature freeze-drying program, and finally obtaining the graphene oxide aerogel, wherein the low-temperature freeze time is 48 hours; an SEM image of the graphene oxide aerogel is shown in FIG. 2, a microstructure is a three-dimensional interconnected porous network structure, and the specific surface area is 121.7 m 2 Per g (as shown in FIG. 3), pore volume 1.04 cm 3 (ii) g (as shown in FIG. 4);
step four: weighing 2g of ferrocene and 1.5g of melamine, and then grinding for 15min to obtain yellow mixed powder;
step five: uniformly spreading 2.5g of mixed powder of ferrocene and melamine in a self-made fumigation vessel (a device shown in figure 1), and uniformly covering 7.5g of freeze-dried graphene oxide aerogel on the mixture of ferrocene and melamine.
Step six: transferring the fumigation to an atmosphere furnace, introducing 200 sccm of nitrogen for 30min, then reducing the flow rate of the nitrogen to 50 sccm, heating to 600 ℃ at the heating rate of 5 ℃/min, preserving the heat for 4h, and then gradually cooling to room temperature under the nitrogen protection condition to obtain 2.2 g of the precursor of the nano iron-based nitrogen-doped graphene composite material.
Step seven: adding the precursor of the nano iron-based nitrogen-doped graphene composite material into 50ml of 0.1M KOH solution, carrying out ultrasonic oscillation for 15min, centrifuging to remove the solvent, then respectively and repeatedly cleaning with deionized water and absolute ethyl alcohol for 2 times, carrying out the last cleaning with a mixed solution of 20% absolute ethyl alcohol and 80% deionized water, centrifuging to remove the solution, and carrying out low-temperature freeze drying to obtain the reduced graphene oxide loaded nano iron oxide ferroelectric catalytic material (figure 5). Wherein the nano-iron oxide has a size of about 2-6nm (as shown in FIG. 6), and a specific surface area of 361.6 m 2 Per g (as shown in FIG. 7), pore volume 1.66 cm 3 (ii) g (as shown in FIG. 8); EDS analysis shows that the composite material contains 7-10% of Fe, 5-7% of N and 15-19% of O, and the contents are shown in tables 1 and 2 and figure 9; the oxygen reduction peak potential of the reduced graphene oxide loaded nano iron oxide electro-catalytic material in the oxygen-saturated 0.1M KOH electrolyte is 0.912V (vs. rhe), and the half-wave potential is 0.824V (vs. rhe) (as shown in fig. 10).
Table 1 test point 1 elemental analysis shown in fig. 9
Table 2 test point 2 elemental analysis shown in fig. 9:
example 2
A preparation method of a graphene-loaded nano iron-based composite electro-catalytic material comprises the following steps:
the method comprises the following steps: 20g of brown graphite oxide prepared by a commercial improved Hummers method (the graphite oxide is stored in a dark vacuum environment, the using time does not exceed 30 days of production date), and then high-purity nitrogen (99.95%) is introduced into 250 ml of absolute ethanol for 30min to realize oxygen removal treatment in the ethanol; and then carrying out centrifugal cleaning on the graphite oxide for 3-5 times to obtain the cleaned graphite oxide.
Step two: taking 480 ml of deionized water (the conductivity is 0.055 mu S/cm) subjected to deoxygenation, adding graphite oxide into the deionized water under the condition of high-speed stirring (1500 rad/min), and stirring at a high speed for 1h to obtain a brown hydrogel-like graphene oxide paste;
step three: placing the graphene oxide paste in a 100 × 150 × 25mm enamel tray, wherein the liquid level height is 20 mm, placing the graphene oxide paste in a low-temperature freeze-drying phase body, closing the sealing, firstly vacuumizing, introducing high-purity nitrogen from an air inlet after the vacuum degree reaches 0.01 MPa, vacuumizing again, repeating the steps for 3 times, then starting a low-temperature freeze-drying program, and finally obtaining the graphene oxide aerogel, wherein the low-temperature freeze time is 48 hours; an SEM image of the graphene oxide aerogel is shown in FIG. 11, wherein the microstructure is a three-dimensional interconnected porous network structure, and the specific surface area is 172.5 m 2 (see FIG. 12), pore volume 1.29 cm 3 (ii) g (FIG. 13);
step four: weighing 4g of acetyl ferrocene and 4.5g of urea, and then grinding for 15min to obtain yellow mixed powder;
step five: uniformly spreading 8.5g of mixed powder of ferrocene and urea in a self-made fumigation utensil (a device shown in figure 1), and uniformly covering 15g of freeze-dried graphene oxide aerogel on the mixture of the acetylferrocene and the urea.
Step six: and (3) moving the fumigation to an atmosphere furnace, introducing 250 sccm of nitrogen for 25min, then reducing the flow rate of the nitrogen to 50 sccm, heating to 700 ℃ at the heating rate of 8 ℃/min, preserving the heat for 4h, and gradually cooling to room temperature under the nitrogen protection condition to obtain 9.8 g of the precursor of the iron nitride-based nitrogen-doped graphene composite material.
Step seven: adding the precursor of the nano iron-based nitrogen-doped graphene composite material into 100ml of 0.5M H 2 SO 4 Performing ultrasonic oscillation for 10min in the solution, centrifuging to remove solvent, respectively cleaning with deionized water and anhydrous ethanol for 2 times, cleaning with 50% anhydrous ethanol + 50% deionized water mixed solution, centrifuging to remove the solution, and cooling at low temperatureAnd (5) freeze-drying to obtain the reduced graphene oxide loaded nano ferroelectric nitride catalytic material (as shown in figure 14). Wherein the nanometer iron nitride has size of about 2-7nm (as shown in FIG. 15), and specific surface area of 354.9 m 2 (as shown in FIG. 16), the pore volume was 1.51 cm 3 (ii) in/g (as shown in FIG. 17); reduced graphene oxide loaded nano ferroelectric nitride catalytic material in oxygen saturated 0.5M H 2 SO 4 The oxygen reduction peak potential in the electrolyte was 0.905V (vs. rhe) and the half-wave potential was 0.817V (vs. rhe) (as shown in fig. 18).
The above embodiments only express specific embodiments of the present application, and the description is specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for those skilled in the art, without departing from the technical idea of the present application, several changes and modifications can be made, which are all within the protection scope of the present application.
Claims (10)
1. A preparation method of a reduced graphene oxide loaded iron-based nanoparticle composite electrocatalytic material is characterized by comprising the following steps:
step 1: preparing an iron/nitrogen precursor: and (2) mixing ferrocene or ferrocene derivatives and nitrogen-containing compounds according to the mass ratio of 1: (3-5) fully grinding and uniformly mixing to obtain an iron/nitrogen precursor mixture;
step 2: synchronously decomposing and fumigating to prepare a composite material precursor: placing the prepared graphene oxide aerogel on the upper layer of a fumigation reaction vessel, placing an iron/nitrogen precursor on the lower layer of the fumigation reaction vessel, placing the fumigation reaction vessel in a high-temperature atmosphere furnace under the protection of inert gas, introducing the inert gas to form an inert atmosphere, heating to 400-1000 ℃ at the speed of 5-10 ℃/min, preserving heat for 2-6h, and then cooling to room temperature in the inert gas atmosphere to obtain a composite material precursor;
and 3, step 3: and (3) cleaning the composite material precursor in strong acid or strong alkali, removing non-catalytic active substances, and freeze-drying to obtain the graphene-loaded nano iron-based composite electrocatalytic composite material.
2. The preparation method of the reduced graphene oxide loaded iron-based nanoparticle composite electrocatalytic material as claimed in claim 1, wherein the ferrocene derivative is a ferrocene derivative with a melting point higher than 120 ℃ and a decomposition temperature higher than 180 ℃, and comprises any one or more of ferrocene derivatives containing acyl, amide and acylhydrazone groups; the nitrogen-containing compound comprises one or more of urea, melamine, polyaniline, p-phenylenediamine and 8-hydroxyquinoline.
3. The preparation method of the reduced graphene oxide-supported iron-based nanoparticle composite electrocatalytic material as claimed in claim 1, wherein the addition amount of the graphene oxide aerogel accounts for 30-40% of the total mass of the iron/nitrogen precursor and the graphene oxide aerogel.
4. The preparation method of the reduced graphene oxide loaded iron-based nanoparticle composite electrocatalytic material as claimed in claim 1, wherein after the fumigation reaction vessel is placed in a high-temperature atmosphere furnace, inert gas is introduced for 25-35min at a gas flow rate of 180-220sccm to form an inert atmosphere; then the flow of the inert gas is reduced to 20-80sccm, and the inert gas is continuously introduced.
5. The method for preparing a reduced graphene oxide loaded iron-based nanoparticle composite electrocatalytic material as claimed in claim 1, wherein the method for preparing the graphene oxide aerogel in the step 2 comprises: firstly, washing graphite oxide by using a nonpolar solvent A, wherein the weight ratio of the graphite oxide is as follows: polar solvent B = (5-8): (92-95), further dissociating the cleaned graphite oxide in a polar solvent B to obtain brown or chestnut gel-like graphene oxide, and freeze-drying at-40 to-60 ℃ for 24-48h in an inert gas atmosphere to obtain the graphene oxide with the surface area of 100-150m 2 Per g, pore volume of 0.5-1.0cm 3 And the viscosity of the graphene oxide aerogel is 300-650mPa & s.
6. The method for preparing a reduced graphene oxide-supported iron-based nanoparticle composite electrocatalytic material as claimed in claim 5, wherein the weight ratio of O/C in the graphite oxide is 1-1.7; the nonpolar solvent A is any one or more of diethyl ether, petroleum ether, tetrahydrofuran and ethanol with the polarity not more than 5.0; the polar solvent B is any one or more of deionized water with polarity more than 8, N-dimethylformamide and methylacetamide.
7. The method for preparing a reduced graphene oxide-supported iron-based nanoparticle composite electrocatalytic material as claimed in claim 1, wherein the strong acid or strong base in step 3 is 0.1M KOH or 0.1M HClO 4 Or 0.5M H 2 SO 4 And (3) solution.
8. The preparation method of the reduced graphene oxide-loaded iron-based nanoparticle composite electrocatalytic material as claimed in claim 1, wherein the fumigation reaction vessel is a cylindrical container made of mullite, graphite, corundum, and silicon carbide, and is divided into two parts, an upper layer and a lower layer, which are communicated with each other through a support arranged in the middle of the container.
9. The reduced graphene oxide-supported iron-based nanoparticle composite electrocatalytic material prepared by the preparation method according to any one of claims 1 to 8.
10. The reduced graphene oxide-supported iron-based nanoparticle composite electrocatalytic material as claimed in claim 9, wherein the reduced graphene oxide-supported iron-based nanoparticles in the composite electrocatalytic material comprise nano iron oxide, iron carbide and iron nitride, the particle size of each of the nano iron oxide, iron carbide and iron nitride is 2-6nm, and the specific surface area of each of the nano iron oxide, iron carbide and iron nitride is greater than 350m 2 Per g, pore volume greater than 1.50cm 3 Per g, the weight content of Fe is 7-10%, the weight content of N is 5-7%, and the weight content of O is 15-19%.
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