CN111450831A - High-performance graphene-loaded mesoporous nickel-iron alloy electrocatalyst and preparation method thereof - Google Patents
High-performance graphene-loaded mesoporous nickel-iron alloy electrocatalyst and preparation method thereof Download PDFInfo
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 29
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- 238000010899 nucleation Methods 0.000 claims abstract description 5
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 4
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- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 3
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- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 3
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- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 3
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Abstract
A high-performance graphene-loaded mesoporous nickel-iron alloy electrocatalyst and a preparation method thereof belong to the technical field of graphene-based electrocatalysts. Taking graphene oxide as an initial carrier, and carrying out Sn reaction2+Sensitization and Pd2+The graphene oxide supported Pd nanoparticles Pd/GO are formed by the activation of the step (2). Ni source NiCl2·6H2O, Fe source FeCl2·4H2O, Pd/GO is dispersed in a lyotropic liquid crystal formed by the surfactant cetyl polyoxyethylene ether (Brij 58). And (3) taking dimethylamine borane (DMAB) as a reducing agent, taking Pd particles on the surface of GO as nucleation centers, and removing Brij58 after the reduction reaction is finished to obtain the graphene-loaded mesoporous ferronickel alloy electrocatalyst. The catalyst combines graphene and a mesoporous nano structure, is beneficial to rapid transmission of electrons and increase of catalytic active sites, and has higher electro-catalytic oxygen evolution performance and excellent stability.
Description
Technical Field
The invention relates to a preparation method and application field of a graphene loaded mesoporous nickel-iron alloy composite material electrocatalyst. The catalyst prepared by the method is particularly suitable for electrocatalytic oxygen evolution reaction, has high activity and high stability, and belongs to the technical field of graphene-based electrocatalysts.
Background
With the increasing global energy demand, the increasing shortage of traditional fossil fuels and the continuous deterioration of natural environment, people have conducted extensive research on efficient energy conversion and storage technologies. Electrochemical Oxygen Evolution Reactions (OERs) have attracted increasing attention and research as half-reactions for the electrolysis of water and metal air batteries. Since the kinetics of the OER process is slow, the development of highly active electrocatalysts is urgently required in order to reduce the applied potential of the electrocatalytic reaction. The Ru/Ir-based electrocatalyst has excellent catalytic activity and stability, and can improve energy conversion efficiency in both acidic and alkaline solutions. However, the high cost of the above noble metal-based catalysts and scarcity of earth resources have hindered their widespread development and application.
The graphene-based catalyst can effectively load various functional nanoparticles, inhibit accumulation and aggregation of the nanoparticles, has good conductivity and is beneficial to electron transmission. In addition, structural adjustment is an effective method for improving catalytic performance. Mesoporous nanomaterials are considered to be one of the most effective strategies for enhancing electrochemical performance due to their large specific surface area, sufficient active sites and uniformly adjustable channels. The unique nanostructure loading the mesoporous metal particles on the surface of the graphene can not only enhance the interface contact of the graphene, but also inhibit the agglomeration of the mesoporous particles, so that the graphene has strong mechanical strength. Meanwhile, the mesoporous structure can expose more electrocatalytic active sites, and the electrocatalytic performance is enhanced. Therefore, the close combination of the mesoporous metal and the graphene can integrate and enhance the advantages of the mesoporous metal and the graphene, and a new idea is provided for the design and development of the OER electrocatalyst. However, obtaining highly uniform mesoporous metals and tightly binding with graphene have great difficulties, and thus the synthesis of mesoporous metal particle/rGO composite nanostructures is extremely challenging.
The invention provides a new synthesis method for preparing a graphene-loaded mesoporous metal alloy nano composite material, and the graphene-loaded mesoporous nickel-iron alloy electrocatalyst with high activity and high stability is synthesized by combining a lyotropic liquid crystal template method and a chemical reduction method.
Disclosure of Invention
The invention aims to provide a high-performance graphene-loaded mesoporous ferronickel composite material electrocatalyst and a preparation method thereof, so that the mesoporous metal alloy-loaded graphene-based electrocatalyst has excellent electrocatalytic oxygen evolution performance. The high-performance graphene-loaded mesoporous nickel-iron alloy composite material electrocatalyst is characterized in that metal alloy with ordered mesopores is dispersedly loaded on the surface of graphene with high surface area to form graphene-loaded mesoporous nickel-iron alloy composite material Ni1- xFexThe thickness of the mesoporous ferronickel alloy is 0-0.20, wherein the whole mesoporous ferronickel alloy is of a spherical structure, and the spherical structure is a mesoporous structure; the graphene and the mesoporous metal alloy form a conductive network which is mutually crosslinked.
The graphene loaded mesoporous nickel-iron alloy composite material electrocatalyst is prepared according to the following steps:
(1) and (3) stripping natural graphite oxide powder by adopting an improved Hummers method to synthesize Graphene Oxide (GO). And repeatedly centrifuging and washing the obtained graphene oxide by using 5% dilute hydrochloric acid and deionized water until the supernatant is neutral so as to remove redundant reactants. And (4) carrying out freeze drying on the graphene oxide after the graphene oxide is collected by centrifugation.
(2) Dispersing the graphene oxide obtained in the step (1) in stannous chloride (SnCl)2) Hydrochloric acid solution (pH 3.0), mixed and stirred for 10 minutes. Cleaning with deionized water for several times, and then adding graphene and SnCl2Palladium chloride (PdCl) is added to the mixed liquid of (1)2) Hydrochloric acid solution (pH 3.0),mix and stir for 5 minutes. Washing with deionized water for several times, and centrifuging and collecting to obtain graphene oxide loaded mesoporous Pd particles (Pd/GO), wherein the graphene oxide: SnCl2：PdCl2Is preferably 9: 16: 2.
(3) firstly, preparing a certain amount of hydrochloric acid solution with pH value of about 2.0-3.0, and then preparing a certain amount of nickel chloride hexahydrate (NiCl)2·6H2O), ferrous chloride tetrahydrate (FeCl)2·4H2O), graphene oxide loaded mesoporous Pd particles (Pd/GO), a hydrochloric acid solution and a nonionic surfactant cetyl polyoxyethylene ether (Brij 58) are continuously heated and stirred until a uniform lyotropic liquid crystal mixture is formed. Wherein NiCl2·6H2O: Pd/GO: aqueous HCl solution: the mass ratio of Brij58 is preferably (1.5-2): 0.025: (2.5-3.5): 5, preferably, the heating temperature of the lyotropic liquid crystal mixture is 60-80 ℃;
(4) adding a certain amount of dimethylamine borane (DMAB) into the lyotropic liquid crystal prepared in the step (3) for reduction, wherein in the reduction stage, the Pd particles on the surface of GO are used as nucleation centers, and reduced Ni and Fe are preferentially deposited and grow around the Pd nanoparticles; after the reduction reaction is finished, the surfactant (Brij 58) is removed by absolute ethyl alcohol to obtain the high-performance graphene loaded mesoporous ferronickel alloy composite nano material (Ni)1-xFex/rGO)。
In order to effectively load mesoporous metal particles on the surface of graphene, graphene oxide is subjected to Sn2+And Pd2+Forming nucleation center Pd particles on the surface of the graphene oxide through sensitization and activation. Graphene-loaded mesoporous nickel-iron alloy composite material (Ni)1-xFex/rGO), wherein x is 0-0.20, and FeCl is added in the step (3)2·4H2O regulation of Ni in lyotropic liquid crystal mixtures2+And Fe2+Atomic molar ratio of (a).
Adding reducing agents dimethylamine borane (DMAB) and NiCl into the lyotropic liquid crystal mixture in the step (4)2The preferable mass ratio of (1) to (1.2). The temperature of the reduction reaction is preferably controlled to be 15-20 ℃.
The material obtained by the invention is used for electrocatalytic oxygen evolution reaction in alkaline solution.
Compared with high-activity commercial RuO (RuO), the performance of the prepared graphene loaded mesoporous nickel-iron alloy composite material is researched by carrying out electrocatalysis oxygen evolution reaction2The catalyst and the graphene loaded mesoporous nickel-iron alloy show high-activity and high-stability electro-catalytic oxygen evolution reaction performance. The electrocatalyst is a graphene-loaded mesoporous ferronickel alloy composite material prepared by adopting a lyotropic liquid crystal template method and a chemical reduction method, and the particle size of mesoporous ferronickel alloy particles is 50 nm. The graphene serving as a conductive matrix has dual functions of loading active substances and inhibiting particle agglomeration, more sites are exposed in a mesoporous structure, and the material has excellent catalytic performance due to the fact that the catalyst has the optimal ferronickel proportion with high activity. The preparation method can adjust the proportion of ferronickel in the mesoporous alloy according to the proportion of nickel chloride and ferrous chloride in the precursor solution, and has the advantages of easily controlled preparation parameters and good repeatability.
Drawings
FIG. 1 shows graphene loaded mesoporous ferronickel (Ni) alloys with different ferronickel ratios prepared in example 11-xFex/rGO) scanning electron micrographs; a to e are Ni/rGO and Ni respectively0.95Fe0.05/rGO、Ni0.90Fe0.10/rGO、Ni0.85Fe0.15/rGO、Ni0.80Fe0.20/rGO。
Fig. 2 is the graphene-supported mesoporous nickel-iron alloy (Ni) with Ni: Fe ═ 85:15 prepared in example 10.85Fe0.05/rGO) high resolution transmission electron microscopy images.
FIG. 3 shows graphene loaded mesoporous ferronickel (Ni) alloys with different ferronickel ratios prepared in example 21-xFexTransmission electron microscopy images of/rGO); a-d respectively correspond to Ni/rGO and Ni0.95Fe0.05/rGO、Ni0.90Fe0.10/rGO、Ni0.80Fe0.20/rGO。
FIG. 4 shows graphene loaded mesoporous ferronickel (Ni) alloys of example 3 with different ferronickel ratios1-xFex/rGO) XRD pattern.
FIG. 5 shows graphene loaded mesoporous ferronickel (Ni) alloys of different ferronickel ratios prepared in example 11-xFexElectrocatalysis of/rGO) in 1M KOH solutionAnd (3) a map of the performance of the oxidation reaction.
Detailed Description
The process of the present invention is further illustrated below with reference to examples. These examples further describe and illustrate embodiments within the scope of the present invention. The examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many variations thereof are possible without departing from the spirit and scope of the invention.
Example 1
The preparation method of the graphene loaded mesoporous nickel-iron alloy comprises the following steps:
(1) and (3) utilizing an improved Hummers method to strip the oxidized natural graphite powder to synthesize Graphene Oxide (GO). And repeatedly centrifuging and washing the obtained graphene oxide by using 5% dilute hydrochloric acid and deionized water until the supernatant is neutral. And (4) collecting the graphene oxide by high-speed centrifugation, and then freeze-drying.
(2) Dispersing the graphene oxide obtained in the step (1) in stannous chloride (SnCl)2) Hydrochloric acid solution (pH 3.0), mixed and stirred for 10 minutes. Cleaning with deionized water for several times, and then adding graphene and SnCl2Palladium chloride (PdCl) is added to the mixed liquid of (1)2) Hydrochloric acid solution (pH. apprxeq.3.0), mixed and stirred for 5 minutes. And washing with deionized water for several times, and centrifuging and collecting to obtain the graphene oxide loaded mesoporous Pd nanoparticles (Pd/GO). Wherein the graphene oxide: SnCl2：PdCl2Is preferably 9: 16: 2.
(3) firstly, preparing a certain amount of hydrochloric acid solution with pH value of about 2.0-3.0, and then preparing a certain amount of nickel chloride hexahydrate (NiCl)2·6H2O), ferrous chloride tetrahydrate (FeCl)2·4H2O), graphene supported mesoporous Pd nanoparticles (Pd/GO), a hydrochloric acid solution and a nonionic surfactant cetyl polyoxyethylene ether (Brij 58) are continuously heated and stirred until a uniform lyotropic liquid crystal mixture is formed. Wherein NiCl2·6H2O: Pd/GO: aqueous HCl solution: the mass ratio of Brij58 is preferably 1.8: 0.025: 3: 5, preferably, the heating temperature of the lyotropic liquid crystal mixture is 60-80 ℃;
(4) adding a quantity of dimethylamine borane (DMAB) to the solution prepared in step (3)In a liquid crystal mixture (reducing agent with NiCl)2The mass ratio of (A) to (B) is 1.1: 1). At a reduction temperature of 15 ℃, the Pd particles on the GO surface act as nucleation centers, and the reduced Ni and Fe preferentially deposit and grow around the Pd particles. After the reduction reaction is finished, the surfactant (Brij 58) is removed by absolute ethyl alcohol, and then the high-performance graphene loaded mesoporous nickel-iron alloy composite nano material (Ni) is obtained1-xFex/rGO)。
(5) Graphene-loaded mesoporous nickel-iron alloy composite material (Ni)1-xFex/rGO), wherein x is 0-0.20, and FeCl is added in the step (3)2·4H2O regulation of Ni in lyotropic liquid crystal mixtures2+And Fe2+The atomic ratio of (a). The experimental procedure was exactly the same as described above. NiCl when x is 0.05, 0.10, 0.15 and 0.20 respectively2·6H2O: the mass ratio of Brij58 is 0.339: 1. 0.321: 1. 0.303: 1 and 0.285: 1.
FIG. 1 is a Scanning Electron Microscope (SEM) image of the product. Scanning Electron Microscope (SEM) images show that metal particles of about 50nm in size are attached to the graphene surface. The Pd nanoparticles on the surface of the graphene oxide serve as nucleation seeds of the mesoporous alloy. Brij58 forms a lyotropic liquid crystal comprising a nickel source, an iron source, and graphene oxide-supported Pd particles. And selectively depositing and growing metal ions in the reduction process to form the graphene loaded mesoporous ferronickel alloy composite nano material. The mesoporous metal alloy with uniform size is dispersed on the surface of the reduced graphene oxide thin layer, which shows that the nano composite structure between the mesoporous bimetallic alloy and the graphene is fully established. As can be seen from a transmission electron microscope (figure 2), the mesoporous has short-range order, the aperture is 3-4 nm, and the particle size of the alloy particles is 50 nm. Fig. 4 is a wide-angle XRD spectrum of the graphene-loaded mesoporous nickel-iron alloy prepared in this embodiment. The broad diffraction peak at 2 θ ═ 21 ° is a characteristic peak of reduced graphene oxide, and the broad diffraction peak at 2 θ ═ 45 ° shows that the alloy is in an amorphous state.
Fig. 5 shows graphene loaded mesoporous nickel-iron alloy Ni prepared in this embodiment1-xFexPolarization curves of/rGO in 1M KOH solutions. From FIG. 5, Ni0.85Fe0.05catalyst/rGO at 10mA cm-2Electric currentThe overpotential of the oxygen evolution reaction of the density is 232mV, which is obviously lower than that of the commercial RuO with high-activity electro-catalysis oxygen evolution reaction2The catalyst (315mV) shows that the prepared graphene loaded mesoporous ferronickel alloy catalyst has higher catalytic activity.
Example 2
The preparation method of the graphene-loaded mesoporous nickel-iron alloy is the same as that in the example 1, except that the reduction reaction temperature in the step (4) is 20 ℃, and the obtained result is basically the same as that in the example 1.
Example 3
The preparation method of the graphene-loaded mesoporous nickel-iron alloy is the same as that of example 1, except that NiCl is used in the step (4)2Mass ratio to reducing agent dimethylamine borane (DMAB) 1: 1, the results obtained are substantially the same as in example 1.
Example 4
The preparation method of the graphene-loaded mesoporous nickel-iron alloy is the same as that of example 1, except that NiCl is used in the step (4)2Mass ratio to reducing agent dimethylamine borane (DMAB) 2: the color of the product prepared by this method is gray, indicating that the amount of reducing agent is small and the metal ions in the lyotropic liquid crystal are not completely reacted.
Example 5
The preparation method of the graphene loaded mesoporous nickel-iron alloy comprises the same steps as the example 1, wherein the step of NiCl2·6H2O: Pd/GO: aqueous HCl solution: the mass ratio of Brij58 is preferably 1.5: 0.025: 3.5: 5. the graphene-supported mesoporous ferronickel catalyst (mNi) with Ni: Fe: 85:15 prepared by the method0.85Fe0.15/rGO) for electrocatalytic oxygen evolution reaction at a current density of 10mA cm-2The oxidation overpotential of water of (1) is 244 mV.
Claims (8)
1. The high-performance graphene-loaded mesoporous nickel-iron alloy composite material electrocatalyst is characterized in that metal alloy with ordered mesopores is dispersedly loaded on the surface of graphene with high surface area to form graphene-loaded mesoporous nickel-iron alloy composite material Ni1-xFex0-0.20 of/rGO, wherein the whole mesoporous ferronickel alloy isSpherical structure, the sphere itself is mesoporous structure.
2. The high-performance graphene-supported mesoporous ferronickel composite electrocatalyst according to claim 1, wherein the particle size of the mesoporous ferronickel particles is 50 nm.
3. A method of preparing an electrocatalyst according to claim 1 or 2, comprising the steps of:
(1) and (3) stripping natural graphite oxide powder by adopting an improved Hummers method to synthesize Graphene Oxide (GO). Repeatedly centrifuging and washing the obtained graphene oxide by using 5% dilute hydrochloric acid and deionized water until the supernatant is neutral so as to remove redundant reactants; carrying out centrifugal collection on graphene oxide, and then freeze-drying;
(2) dispersing the graphene oxide obtained in the step (1) in stannous chloride (SnCl)2) Hydrochloric acid solution, mixing and stirring for 10 minutes; cleaning with deionized water for several times, and then adding graphene and SnCl2Palladium chloride (PdCl) is added into the mixed liquid2) Mixing and stirring the hydrochloric acid solution for 5 minutes; washing with deionized water for several times, and centrifuging and collecting to obtain graphene oxide loaded mesoporous Pd particles (Pd/GO), wherein the graphene oxide: SnCl2：PdCl2Is preferably 9: 16: 2;
(3) firstly, preparing a certain amount of hydrochloric acid solution with pH value of 2.0-3.0, and then preparing a certain amount of nickel chloride hexahydrate (NiCl)2·6H2O), ferrous chloride tetrahydrate (FeCl)2·4H2O), graphene oxide loaded mesoporous Pd particles (Pd/GO), a hydrochloric acid solution and a nonionic surfactant cetyl polyoxyethylene ether (Brij 58) are continuously heated and stirred until a uniform lyotropic liquid crystal mixture is formed; wherein NiCl2·6H2O: Pd/GO: aqueous HCl solution: the mass ratio of Brij58 is preferably (1.5-2): 0.025: (2.5-3.5): 5, preferably, the heating temperature of the lyotropic liquid crystal mixture is 60-80 ℃;
(4) adding a certain amount of dimethylamine borane (DMAB) into the lyotropic liquid crystal prepared in the step (3) for reduction, wherein in the reduction stage, Pd particles on the surface of GO are used asThe reduced Ni and Fe are preferentially deposited and grown around the Pd nanoparticles as nucleation centers; after the reduction reaction is finished, the surfactant (Brij 58) is removed by absolute ethyl alcohol to obtain the high-performance graphene loaded mesoporous ferronickel alloy composite nano material (Ni)1-xFex/rGO)。
4. The process according to claim 3, characterized in that the pH of the hydrochloric acid solution of step (2) is ≈ 3.0.
5. The method of claim 3, wherein the graphene oxide is passed through Sn2+And Pd2+Forming nucleation center Pd particles on the surface of the graphene oxide by sensitization and activation; graphene-loaded mesoporous nickel-iron alloy composite material Ni1-xFexIn the/rGO, x is 0-0.20, and FeCl is added in the step (3)2·4H2O regulation of Ni in lyotropic liquid crystal mixtures2+And Fe2+Atomic molar ratio of (a).
6. A method according to claim 3, wherein the reducing agents dimethylamine borane (DMAB) and NiCl are added to the lyotropic liquid crystal mixture in step (4)2The preferable mass ratio of (1) to (1.2).
7. The method according to claim 3, wherein the temperature of the reduction reaction in the step (4) is controlled to 15 to 20 ℃.
8. Use of the electrocatalyst according to claim 1 or 2 for electrocatalytic oxygen evolution reactions in alkaline solutions.
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