CN113718281A - Graphene quantum dot/MXene nanosheet two-dimensional composite material and preparation method and application thereof - Google Patents
Graphene quantum dot/MXene nanosheet two-dimensional composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN113718281A CN113718281A CN202111130565.8A CN202111130565A CN113718281A CN 113718281 A CN113718281 A CN 113718281A CN 202111130565 A CN202111130565 A CN 202111130565A CN 113718281 A CN113718281 A CN 113718281A
- Authority
- CN
- China
- Prior art keywords
- mxene
- quantum dot
- composite material
- graphene quantum
- dimensional composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides a graphene quantum dot/MXene nanosheet two-dimensional composite material as well as a preparation method and application thereof, and belongs to the technical field of catalysts containing carbon compounds. The preparation method comprises the steps of etching carbon aluminum titanium by lithium fluoride and hydrochloric acid to obtain an MXene material, and ultrasonically dispersing the MXene material in a glycol solution to obtain an MXene nanosheet dispersion liquid; and adding graphene oxide quantum dots into the MXene nanosheet dispersion liquid, and carrying out hydrothermal reaction, dialysis water washing and freeze drying on the obtained mixed solution to obtain the graphene quantum dot/MXene nanosheet two-dimensional composite material. The graphene quantum dot/MXene nanosheet two-dimensional composite material is used as a hydrogen evolution catalyst, and has excellent catalytic performance and stability.
Description
Technical Field
The invention belongs to the technical field of catalysts containing carbon compounds, and particularly relates to a graphene quantum dot/MXene nanosheet two-dimensional composite material and a preparation method and application thereof.
Background
In a new round of energy revolution, hydrogen energy becomes the first choice for developing new energy technology in countries around the world due to the advantages of rich source, high energy density, cleanness, no pollution, renewability, wide application and the like. Water electrolysis is a very promising hydrogen production technology, however, the cathodic reduction Hydrogen Evolution (HER) reaction involved in the water electrolysis process requires a high overpotential, which greatly limits the production efficiency of hydrogen. In order to reduce the overpotential of water decomposition and increase the reaction rate, the development and utilization of a high-performance HER electrode catalyst is an effective way, which becomes the key point for the commercial application of the water electrolysis hydrogen production technology. To date, precious metals (e.g., Pt, Ir, Ru, etc.) are considered the most effective HER catalysts, however their high cost and scarcity limit their use on a large scale in practical production. Therefore, the development of an electrocatalyst with high catalytic activity and low cost is the biggest challenge in the field of hydrogen production by water electrolysis at present.
Two-dimensional transition metal carbon/nitride (MXene) as one member of a two-dimensional material family not only naturally has an ultra-large specific surface area and an ultrathin nanosheet structure similar to graphene, but also has a series of other additional structural advantages including excellent metal conductivity, abundant surface functional groups, good hydrophilicity, good electrochemical stability and the like. Compared with the traditional nano carbon material, the surface chemical property of MXene is more active, and richer catalytic active sites can be provided; compared with Transition Metal Disulfides (TMDs) with only edge point catalytic activity, MXene can be catalyzed in a wider surface area and shows higher catalytic efficiency. In addition, when compounded with other catalytic materials, the surface groups of MXene can serve as anchoring sites, ensuring stable binding between MXene and the compound. In view of the above, MXene is expected to become a candidate material of the next-generation non-noble metal hydrogen evolution catalyst.
On the other hand, the graphene quantum dots are a quasi-zero-dimensional nano material, have excellent quantum confinement effect and edge effect, and can not generate accumulation and aggregation phenomena between graphene layers due to strong intermolecular force. Particularly, the graphene quantum dots not only have the structure and properties of graphene, such as large specific surface area, good chemical stability and the like, but also have abundant edge defect positions due to the unique quasi-zero-dimensional structure, so that a large number of active sites can be provided for electrocatalytic reaction. In addition, a large number of carboxyl functional groups on the surface of the graphene quantum dot can enable the water solubility of the graphene quantum dot to be better, and the graphene quantum dot can be conveniently coupled or hybridized with other carrier materials, so that the electrocatalytic performance of the material is further improved.
Considering that the graphene quantum dots have a large number of active edge sites and a rich defect structure, if the graphene quantum dots are combined with a typical MXene material (Ti)3C2Tx) nano-sheets are combined, so that the electro-catalysis performance of the catalyst material is expected to be improved to a great extent. So far, in the field of electrocatalysis, some progress has been made on the research work of MXene materials and compounds thereof or graphene quantum dots as hydrogen evolution catalysts. However, the research on the graphene quantum dot/MXene composite as the electrocatalyst is still in the beginning stage, and particularly, the research on the synthesis of the graphene quantum dot/MXene two-dimensional composite catalyst and the application of the graphene quantum dot/MXene two-dimensional composite catalyst as the hydrogen evolution catalyst is not reported.
CN111744519A discloses a preparation method of a three-dimensional MXene-based carrier hydrogen evolution catalyst, wherein an MXene-carbon material three-dimensional composite carrier is prepared from an MXene material and a carbon material, catalytic active particles are loaded, and the three-dimensional MXene-based carrier hydrogen evolution catalyst is obtained through the steps of reduction, water washing, drying and the like. Wherein the catalytically active particles are H2PtCl6·6H2O、PdCl2、Na2PdCl4、K2PdCl6、NiCl2、CoCl2、CuCl2、ZnCl2Any one of the above. I.e. the one which plays the main catalytic role in the hydrogen evolution catalystNot MXene-carbon material composites.
Disclosure of Invention
The invention provides a graphene quantum dot/MXene nanosheet two-dimensional composite material and a preparation method thereof, aiming at solving the problems of high cost and scarcity of a noble metal hydrogen evolution catalyst, and the two-dimensional composite material is used as the hydrogen evolution catalyst to obtain a good effect. According to the method, MXene nanosheets are used as templates, graphene quantum dots are deposited on the surfaces of the MXene nanosheets, and the prepared two-dimensional composite material serving as an electrode catalyst has the advantages of high catalytic activity, good stability and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a graphene quantum dot/MXene nanosheet two-dimensional composite material is composed of 3-10% of graphene quantum dots and 90-97% of MXene nanosheets in percentage by mass.
The preparation method of the graphene quantum dot/MXene two-dimensional composite material comprises the following steps:
s1, etching aluminum titanium by using lithium fluoride and hydrochloric acid, performing ultrasonic treatment and centrifugal washing to obtain an MXene material, dispersing the MXene material in water, performing ultrasonic stripping, performing freeze drying to obtain an MXene nanosheet, and performing ultrasonic dispersion on the MXene nanosheet in a glycol solution to obtain an MXene nanosheet dispersion liquid;
s2, adding a graphene oxide quantum dot solution into the MXene nanosheet dispersion liquid obtained in the step S1, and stirring and mixing uniformly to obtain a graphene oxide quantum dot/MXene nanosheet binary composite solution, wherein the addition amount of the graphene oxide quantum dot solution enables the mass of the graphene quantum dot to be 3-10% of the mass of the graphene quantum dot/MXene nanosheet two-dimensional composite material, and the mass of the MXene nanosheet in the MXene nanosheet dispersion liquid is 90-97% of the mass of the graphene quantum dot/MXene nanosheet two-dimensional composite material;
s3, carrying out hydrothermal reaction on the binary compound solution obtained in the step S2, dialyzing and washing the water solution obtained after the reaction, and carrying out freeze drying to obtain the graphene quantum dot/MXene nanosheet two-dimensional composite material.
The graphene quantum dot/MXene nanosheet two-dimensional composite material is prepared by taking MXene nanosheets as a carrier material and taking graphene quantum dots as a modifying material. Firstly, preparing an MXene material by a chemical etching method, and ultrasonically stripping the MXene material to obtain a single-layer or few-layer MXene nanosheet; dispersing the single-layer or few-layer MXene nanosheets in an ethylene glycol solution, then adding graphene oxide quantum dots, and reducing the graphene oxide quantum dots into graphene quantum dots through ethylene glycol; and finally, combining the MXene nanosheets and the graphene quantum dots by adopting a hydrothermal reaction, and loading more and more graphene quantum dots on the MXene nanosheets to form a stable two-dimensional structure along with the rise of the temperature.
The graphene quantum dots and the MXene nanosheets are self-assembled into a two-dimensional stable structure together by a bottom-up solvothermal reaction method, the wide surface area of the MXene nanosheets can facilitate the dispersion of the graphene quantum dots, and surface groups of the MXene nanosheets can provide rich growth sites for the deposition of the graphene quantum dots, so that the composite has rapid ion transfer capability and an efficient electrochemical active surface due to the high conductivity and rich defect structures of the MXene nanosheets and the graphene quantum dots, and better electrochemical properties can be obtained.
Compared with the conventional graphene oxide (or graphene)/MXene composite material, the zero-dimensional graphene quantum dot component selected by the invention has richer boundary defect structures, so that the quantity of catalytic active sites is more, and the whole electrocatalysis performance of the material is greatly improved.
Preferably, the glycol solution in step S1 is prepared by mixing glycol and water in a volume ratio of 1: 1;
preferably, the concentration of the graphene oxide quantum dot solution in the step S2 is 1 mg/mL;
preferably, in step S2, the addition amount of the graphene oxide quantum dot solution is such that the mass of the graphene quantum dot accounts for 5% of the mass of the graphene quantum dot/MXene nanosheet two-dimensional composite material, and the mass of the MXene nanosheet in the MXene nanosheet dispersion solution accounts for 95% of the mass of the graphene quantum dot/MXene nanosheet two-dimensional composite material.
Preferably, the hydrothermal reaction conditions in step S3 are: reacting for 8-12 h at 90-120 ℃.
Preferably, the dialysis water washing time in the step S3 is 3-5 d, and the pressure of freeze drying is less than or equal to 200 Pa.
Preferably, the conditions for stirring and mixing uniformly in step S2 are as follows: stirring for 1-2 h at 10-30 ℃.
Preferably, the reaction conditions of the etching in step S1 are: reacting for 36-44 h at 25-40 ℃; the concentration of the hydrochloric acid is 8-10 mol/L; the mass ratio of the lithium fluoride to the hydrogen chloride in the hydrochloric acid to the carbon-aluminum-titanium is 1:6.6: 2.
Preferably, the conditions of the centrifugal water washing in step S1 are: the centrifugal speed is 4500-7000 rpm, and the supernatant is washed until the pH value is 6-7.
Preferably, the ultrasonic peeling conditions in step S1 are: and (3) ultrasonic stripping time is 1-1.5 h, argon is continuously introduced while ultrasonic treatment is carried out, centrifugal screening is carried out at the rotating speed of 6000-8000 rpm after ultrasonic treatment is finished, and the centrifugal supernatant is taken for freeze drying to obtain the single-layer or few-layer MXene nanosheet.
Preferably, the concentration of the MXene nanosheet dispersion in step S1 is 5-10 g/L.
Preferably, the conditions of the ultrasonic dispersion in step S1 are: performing ultrasonic treatment at 10-30 ℃ for 1-4 h.
According to the invention, the graphene quantum dot/MXene two-dimensional composite material prepared by adopting any one of the technical schemes is used as a hydrogen evolution catalyst, and has excellent catalytic performance and durability under an acidic condition.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the preparation method of the graphene quantum dot/MXene two-dimensional composite material, the prepared hydrogen evolution catalyst has the advantages of high catalytic activity, good stability, good cyclicity and the like.
2. The preparation method provided by the invention is simple and controllable, has good repeatability and low cost, and is beneficial to large-scale industrial production.
Drawings
FIG. 1 is a schematic flow chart of the preparation of a graphene quantum dot/MXene two-dimensional composite material according to the present invention;
fig. 2 is a raman spectrum of the graphene quantum dot/MXene two-dimensional composite material prepared in embodiment 2 of the present invention;
fig. 3A is a field emission scanning electron microscope (FE-SEM) photograph of the graphene quantum dot/MXene two-dimensional composite material prepared in example 2 of the present invention;
FIG. 3B is a 2-fold enlarged view of FIG. 3A;
fig. 4A is a Transmission Electron Microscope (TEM) photograph of the graphene quantum dot/MXene two-dimensional composite material prepared in example 2 of the present invention;
FIG. 4B is a view of FIG. 4A at a magnification of 4;
FIG. 5 shows graphene quantum dot/MXene two-dimensional composite materials (GQD) prepared in examples 1 to 3 and comparative examples 1 to 2 of the present inventionS/MXene), the graphene/MXene two-dimensional composite material prepared in comparative example 3, the graphene oxide quantum dot/MXene two-dimensional composite material prepared in comparative example 4, and the Graphene Oxide Quantum Dot (GOQD) prepared in comparative example 5S) MXene (Ti) prepared in comparative example 63C2Tx) material as hydrogen evolution catalyst at 0.5mol/L H2SO4Linear sweep voltammograms in solution;
FIG. 6 shows graphene quantum dot/MXene two-dimensional composite materials (GQD) prepared in examples 1 to 3 and comparative examples 1 to 2 of the present inventionS/MXene), the graphene/MXene two-dimensional composite material prepared in comparative example 3, the graphene oxide quantum dot/MXene two-dimensional composite material prepared in comparative example 4, and the Graphene Oxide Quantum Dot (GOQD) prepared in comparative example 5S) Mxene (Ti) prepared in comparative example 63C2Tx) material as hydrogen evolution catalyst at 0.5mol/L H2SO4Tafel plot in solution;
fig. 7 shows a graphene quantum dot/MXene two-dimensional composite material (GQD) prepared in embodiment 2 of the present inventionSMXene) time potential test curve;
fig. 8 shows a graphene quantum dot/MXene two-dimensional composite material (GQD) prepared in embodiment 2 of the present inventionS/MXene).
Detailed Description
The technical solution of the present invention is described in detail and fully with reference to the following examples, it is obvious that the described examples are only a part of the examples of the present invention, and not all of the examples. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention. Any equivalent changes or substitutions by those skilled in the art according to the following embodiments are within the scope of the present invention.
Example 1
The embodiment provides a graphene quantum dot/MXene nanosheet two-dimensional composite material, which is composed of 3% of graphene quantum dots and 97% of MXene nanosheets in percentage by mass.
As shown in fig. 1, the preparation method of the graphene quantum dot/MXene nanosheet two-dimensional composite material in this embodiment is as follows:
s1, preparing MXene nanosheet dispersion liquid: etching 2g of aluminum titanium carbide by using 1g of lithium fluoride and 22.5mL of 8mol/L hydrochloric acid at 25 ℃, wherein the etching reaction time is 44 h; then centrifugally washing the supernatant at 4500rpm until the pH value of the supernatant is 7; adding the obtained multilayer MXene material into 40mL of distilled water, ultrasonically stripping for 1h, continuously introducing argon for protection while ultrasonically treating, centrifugally screening at the rotating speed of 7000rpm after ultrasonically treating, and freeze-drying the precipitate at-42 ℃ under the condition of 200 Pa; dissolving the obtained single-layer or few-layer MXene nanosheets in 80mL of 50% volume fraction ethylene glycol solution, and performing ultrasonic dispersion for 4 hours at 10 ℃ to obtain 6g/L MXene nanosheet dispersion liquid;
s2, adding 19mL of 1mg/mL graphene oxide quantum dot solution into the MXene nanosheet dispersion liquid obtained in the step S1, stirring for 1h at 20 ℃, and uniformly mixing to obtain a graphene oxide quantum dot/MXene nanosheet binary composite solution;
s3, placing the binary compound solution obtained in the step S2 at 90 ℃ for hydrothermal reaction for 12 hours to obtain a graphene quantum dot/MXene nanosheet binary compound solution, then dialyzing and washing for 4 days by using a dialysis membrane with the pore size of 0.45 mu m, and freeze-drying under the condition that the pressure is less than or equal to 200Pa to obtain the graphene quantum dot/MXene nanosheet two-dimensional composite material.
Example 2
The embodiment provides a graphene quantum dot/MXene nanosheet two-dimensional composite material, which is composed of 5% of graphene quantum dots and 95% of MXene nanosheets in percentage by mass.
As shown in fig. 1, the preparation method of the graphene quantum dot/MXene nanosheet two-dimensional composite material in this embodiment is as follows:
s1, preparing MXene nanosheet dispersion liquid: etching 2g of aluminum titanium carbide by using 1g of lithium fluoride and 20mL of 9mol/L hydrochloric acid at 25 ℃, wherein the etching reaction time is 36 h; then centrifugally washing the supernatant at 6000rpm until the pH value of the supernatant is 6; adding the obtained multilayer MXene material into 40mL of distilled water, ultrasonically stripping for 1h, continuously introducing argon for protection while ultrasonically treating, centrifugally screening at the rotating speed of 8000rpm after ultrasonically treating, and freeze-drying the precipitate at-42 ℃ under 200 Pa; dissolving the obtained single-layer or few-layer MXene nanosheets in 80mL of 50% volume fraction ethylene glycol solution, and performing ultrasonic dispersion for 3h at 20 ℃ to obtain 5g/L MXene nanosheet dispersion liquid;
s2, adding 26mL of 1mg/mL graphene oxide quantum dot solution into the MXene nanosheet dispersion liquid obtained in the step S1, stirring for 2 hours at 10 ℃, and uniformly mixing to obtain a graphene oxide quantum dot/MXene nanosheet binary composite solution;
s3, placing the binary compound solution obtained in the step S2 at 100 ℃ for a hydrothermal reaction for 10 hours to obtain a graphene quantum dot/Mxene nanosheet binary compound solution, then dialyzing and washing for 3 days by using a dialysis membrane with the pore size of 0.45 mu m, and freeze-drying under the condition that the pressure is less than or equal to 200Pa to obtain the graphene quantum dot/MXene nanosheet two-dimensional composite material.
Fig. 2 is a raman spectrogram of the graphene quantum dot/MXene nanosheet two-dimensional composite material prepared in the embodiment, and characteristic peaks of the MXene nanosheet and the graphene quantum dot can be clearly seen from the raman spectrogram, so that the graphene quantum dot and the MXene nanosheet are confirmed to be simultaneously present in the product, and the graphene quantum dot is successfully loaded on the MXene nanosheet.
Fig. 3A is a field emission scanning electron microscope (FE-SEM) photograph of the graphene quantum dot/MXene nanosheet two-dimensional composite material prepared in this embodiment, and it can be seen from the photograph that the MXene nanosheet has an obvious two-dimensional layered structure, and can provide a large number of binding sites for the tiny graphene quantum dots; fig. 3B is a 2-fold enlarged view of fig. 3A, and it can be clearly seen from the figure that the graphene quantum dots are successfully loaded on the MXene nanosheets and the coverage is very uniform.
Fig. 4A is a transmission electron microscope image of the graphene quantum dot/MXene nanosheet two-dimensional composite material prepared in the embodiment, and further proves that the graphene quantum dots are well dispersed on the MXene nanosheets and have no obvious agglomeration phenomenon; fig. 4B is a 4-fold enlarged view of fig. 4A, from which the graphene quantum dot lattice fringes can be clearly seen.
The test results of fig. 2 to fig. 4B show that the graphene quantum dot/MXene nanosheet two-dimensional composite material prepared by the method has a very large specific surface area, and the graphene quantum dots are uniformly distributed on the MXene nanosheet base surface.
Example 3
The embodiment provides a graphene quantum dot/MXene nanosheet two-dimensional composite material, which is composed of 10% of graphene quantum dots and 90% of MXene nanosheets by mass percent.
As shown in fig. 1, the preparation method of the graphene quantum dot/MXene nanosheet two-dimensional composite material in this embodiment is as follows:
s1, preparing MXene nanosheet dispersion liquid: etching 2g of aluminum titanium carbide by using 1g of lithium fluoride and 18mL of 10mol/L hydrochloric acid at 25 ℃, wherein the etching reaction time is 38 h; then centrifugally washing the supernatant at 7000rpm until the pH value of the supernatant is 7; adding the obtained multilayer MXene material into 40mL of distilled water, ultrasonically stripping for 1.5h, continuously introducing argon for protection while ultrasonically treating, centrifugally screening at the rotating speed of 6000rpm after ultrasonically treating, and freeze-drying the precipitate at-42 ℃ under the condition of 200 Pa; dissolving the obtained single-layer or few-layer MXene nanosheets in 80mL of 50% volume fraction ethylene glycol solution, and performing ultrasonic dispersion for 1h at 30 ℃ to obtain a 10g/L MXene nanosheet dispersion liquid;
s2, adding 111mL of 1mg/mL graphene oxide quantum dot solution into the MXene dispersion liquid obtained in the step S1, stirring for 0.5h at 30 ℃, and uniformly mixing to obtain a graphene oxide quantum dot/Mxene nanosheet binary composite solution;
s3, placing the binary compound solution obtained in the step S2 at 120 ℃ for hydrothermal reaction for 8 hours to obtain a graphene quantum dot/MXene nanosheet binary compound solution, then dialyzing and washing for 5 days by using a dialysis membrane with the pore size of 0.45 mu m, and freeze-drying under the condition that the pressure is less than or equal to 200Pa to obtain the graphene quantum dot/MXene nanosheet two-dimensional composite material.
Comparative example 1
The comparative example provides a graphene quantum dot/MXene nanosheet two-dimensional composite material, which consists of 1% of graphene quantum dots and 99% of MXene nanosheets in percentage by mass.
The preparation method of the graphene quantum dot/Mxene nanosheet two-dimensional composite material in the comparative example is basically the same as that in example 2, except that: and (4) adding 5mL of 1mg/mL graphene oxide quantum dot solution into the MXene nanosheet dispersion liquid obtained in the step S1, stirring for 2 hours at 10 ℃, and uniformly mixing to obtain a graphene oxide quantum dot/MXene nanosheet binary composite solution.
Comparative example 2
The comparative example provides a graphene quantum dot/MXene nanosheet two-dimensional composite material, which consists of 12% of graphene quantum dots and 88% of MXene nanosheets in percentage by mass.
The preparation method of the graphene quantum dot/MXene two-dimensional composite material in the comparative example is basically the same as that in example 2, except that: and (4) adding 69mL of 1mg/mL graphene oxide quantum dot solution into the MXene nanosheet dispersion liquid obtained in the step S1, stirring for 2 hours at 10 ℃, and uniformly mixing to obtain a graphene oxide quantum dot/MXene nanosheet binary composite solution.
Comparative example 3
The preparation method of the graphene/MXene nanosheet two-dimensional composite material prepared in the comparative example is basically the same as that of the embodiment 2, and the difference is that: graphene oxide nanosheets are added in step S2.
Comparative example 4
The preparation method of the graphene oxide quantum dot/MXene nanosheet two-dimensional composite material prepared in the comparative example is basically the same as that of the embodiment 2, and the difference is that: and step S1, dissolving the obtained single-layer or few-layer MXene nanosheets in 80mL of water, and ultrasonically dispersing for 3h at 20 ℃ to obtain MXene nanosheet dispersion liquid with the concentration of 5 g/L.
Comparative example 5
The comparative example is pure graphene oxide quantum dots purchased from Jiangsu Xiancheng nano material science and technology limited.
Comparative example 6
The comparative example prepared single-layer or few-layer MXene nanosheets, which were prepared in the same manner as the single-layer or few-layer MXene nanosheets prepared in step S1 of example 2:
etching 2g of aluminum titanium carbide by using 1g of lithium fluoride and 20mL of 9mol/L hydrochloric acid at 25 ℃, wherein the etching reaction time is 36 h; then centrifugally washing the supernatant at 6000rpm until the pH value of the supernatant is 6; adding the obtained multilayer MXene material into 40mL of distilled water, ultrasonically stripping for 1h, continuously introducing argon gas for protection while ultrasonically treating, centrifugally screening at the rotating speed of 8000rpm after ultrasonically treating, and freeze-drying the precipitate at-42 ℃ and 200Pa to obtain the monolayer or few-layer MXene nanosheet.
Application example
1. Catalytic activity as hydrogen evolution catalyst
The graphene quantum dot/MXene two-dimensional composite material prepared in the examples 1 to 3 and the comparative examples 1 to 2, the graphene/MXene two-dimensional composite material prepared in the comparative example 3, the graphene oxide quantum dot/MXene two-dimensional composite material prepared in the comparative example 4, the graphene oxide quantum dot in the comparative example 5 and the MXene nanosheet in the comparative example 6 are used as hydrogen evolution reaction catalysts, and the catalytic activities of the graphene quantum dot/MXene two-dimensional composite material and the MXene nanosheet are tested. The test conditions were as follows:
electrochemical tests are carried out on a CHI760E electrochemical workstation, and the test system is a conventional three-electrode system, wherein a carbon rod is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and a glassy carbon electrode coated with an active substance and having a diameter of 3mm is used as a working electrode.
The preparation process of the working electrode comprises the following steps: 2mg of the catalyst powder was weighed and dispersed in a mixed solution of 0.5mL of deionized water, 0.5mL of ethanol and 0.05mL of Nafion (perfluorosulfonic acid membrane), and subjected to ultrasonication for 30 min. And (3) respectively dropwise adding 5 mu L of the dispersion liquid of the graphene quantum dot/MXene two-dimensional composite material prepared in the embodiments 1-3 on the surface of the glassy carbon electrode, drying at normal temperature for 0.5 hour, and then testing.
The catalytic activity of the catalyst in the hydrogen evolution reaction was evaluated by Linear Sweep Voltammetry (LSV) and the electrolyte was 0.5mol/LH2SO4The scanning rate of the solution is 20mV.s-1. The stability of the catalyst was evaluated by chronopotentiometry at a constant potential and the catalyst was tested for tolerance by a long-term cycling test of 2000 cycles. The conductivity of the catalyst was investigated by means of an electrochemical AC impedance test, with a frequency range of up to 1X 1050.02Hz and an amplitude of 10 mV.
FIG. 5 shows graphene quantum dot/MXene two-dimensional composite materials (GQD) prepared in examples 1 to 3 and comparative examples 1 to 2 of the present inventionS/MXene), the graphene/MXene two-dimensional composite material prepared in comparative example 3, the graphene oxide quantum dot/MXene two-dimensional composite material prepared in comparative example 4, the graphene oxide quantum dot prepared in comparative example 5 and the MXene nanosheet prepared in comparative example 6 as hydrogen evolution catalyst at the concentration of 0.5mol/L H2SO4Linear sweep voltammograms in solution. As can be seen from the figure, the initial overpotential of the catalyst with 5% graphene quantum dot loading is the lowest, and the cathode current rapidly increases at a larger negative potential, and compared with other catalysts with different graphene quantum dot loading, the current increase trend of the catalyst prepared in example 2 is more significant, which indicates that the catalyst has more excellent HER catalytic activity. In sharp contrast, the graphene oxide quantum dots in comparative example 5 and the MXene nanosheets prepared in comparative example 6 have small overpotential variation amplitude and relatively very limited catalytic activity due to the deficiency of active sites. When the graphene quantum dot/MXene two-dimensional composite material prepared in the comparative examples 1-2 is used as a hydrogen evolution catalyst, although the overpotential change amplitude is larger than that of the single material in the comparative examples 5-6 when the single material is used as a catalyst, the overpotential change amplitude is not larger than that of the graphene quantum dot/MXene two-dimensional composite material in the examples 1-3. graphene/MXene nanosheet two-dimensional composite material prepared in comparative example 3 andwhen the graphene oxide quantum dot/MXene nanosheet two-dimensional composite material prepared in the comparative example 4 is used as a hydrogen evolution catalyst, the overpotential is higher than that in the example 2, and the hydrogen evolution catalytic performance is obviously inferior to that in the example 2.
In order to further verify the catalytic activity of the materials of the embodiments and the comparative examples when used as a hydrogen evolution catalyst, a corresponding Tafel slope is calculated in fig. 6, and it can be seen from the graph that when the graphene quantum dot/MXene two-dimensional composite material is used as a catalyst, the Tafel slope is smaller than that when a single graphene oxide quantum dot or an MXene nanosheet is used as a catalyst, which indicates that the graphene quantum dot/MXene two-dimensional composite material has higher catalytic activity. From the data of examples 1 to 3 and comparative examples 1 to 2, it can be seen that as the content of the graphene quantum dots increases, the catalytic performance of the composite catalyst gradually increases, when the loading of the graphene quantum dots reaches 5%, the HER activity is highest, and when the loading of the graphene quantum dots continues to increase to 10%, the catalytic activity of the catalyst decreases, which may be due to stacking and aggregation phenomena caused by excessive graphene quantum dots. When the loading of the graphene quantum dots is 1% (below 3%), it is possible that the catalytic activity is not significantly enhanced compared to that of a single MXene material due to too few active sites, and similarly, when the loading of the graphene quantum dots is 12% (above 10%), the catalytic activity is comparable to that of an MXene material without the added graphene quantum dots due to too much aggregation. In comparative example 3, the graphene nanosheet is used for replacing the graphene quantum dot and the MXene nanosheet to form the composite material, the Tafel slope is obviously larger than that in example 2, and the hydrogen evolution catalytic performance of the composite material is not as good as that in example 2, probably because the graphene nanosheets are easier to stack and agglomerate. In comparative example 4, the graphene oxide quantum dots are used for replacing the graphene quantum dots to form a composite material with MXene nanosheets, the Tafel slope is larger than that in example 2, and the hydrogen evolution catalytic performance is also lower than that in example 2, because the conductivity and the activity of the graphene oxide quantum dots are not as good as those of the graphene quantum dots. Therefore, the graphene quantum dots and the MXene nanosheets are used to form the two-dimensional composite material, and the composition ratio of the graphene quantum dots and the MXene nanosheets is within the range defined by the invention, so that the graphene quantum dots and the MXene nanosheets have excellent hydrogen evolution catalytic performance.
2. Electrochemical stability as hydrogen evolution catalyst
The electrochemical stability of the graphene quantum dot/MXene two-dimensional composite material prepared in example 2 when used as a hydrogen evolution catalyst is tested by adopting a chronopotentiometric method. As shown in FIG. 7, the graphene quantum dot/MXene two-dimensional composite material as a catalyst is kept at 12mA · cm for 10000s of test time-2The current density of (a) indicates that it has good catalytic stability. As shown in fig. 8, it can be clearly observed that after 2000 cycles of the test, the LSV curve is almost unchanged, which indicates that the graphene quantum dot/MXene two-dimensional composite material has excellent durability in the long-term electrochemical catalysis process under the acidic condition.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. The present invention may be subject to various modifications and changes by any person skilled in the art. Any simple equivalent changes and modifications made in accordance with the protection scope of the present application and the content of the specification are intended to be included within the protection scope of the present invention.
Claims (10)
1. The graphene quantum dot/MXene nanosheet two-dimensional composite material is characterized by comprising 3-10% of graphene quantum dots and 90-97% of MXene nanosheets in percentage by mass.
2. The preparation method of the graphene quantum dot/MXene nanosheet two-dimensional composite material of claim 1, comprising the steps of:
s1, etching aluminum titanium by using lithium fluoride and hydrochloric acid, performing ultrasonic treatment and centrifugal washing to obtain an MXene material, dispersing the MXene material in water, performing ultrasonic stripping, performing freeze drying to obtain an MXene nanosheet, and performing ultrasonic dispersion on the MXene nanosheet in a glycol solution to obtain an MXene nanosheet dispersion liquid;
s2, adding a graphene oxide quantum dot solution into the MXene nanosheet dispersion liquid obtained in the step S1, stirring and mixing uniformly to obtain a graphene oxide quantum dot/MXene nanosheet binary composite solution, wherein the graphene oxide quantum dot solution is added in an amount which enables the mass of the graphene quantum dot to be 3-10% of the mass of the graphene quantum dot/MXene nanosheet two-dimensional composite material;
s3, carrying out hydrothermal reaction on the binary compound solution obtained in the step S2, dialyzing and washing the water solution obtained after the reaction, and carrying out freeze drying to obtain the graphene quantum dot/MXene nanosheet two-dimensional composite material.
3. The method for preparing the graphene quantum dot/MXene nanosheet two-dimensional composite material according to claim 2, wherein the graphene oxide quantum dot solution is added in an amount such that the mass of the graphene quantum dot accounts for 5% of the mass of the graphene quantum dot/MXene nanosheet two-dimensional composite material in step S2.
4. The preparation method of the graphene quantum dot/MXene nanosheet two-dimensional composite material according to claim 2, wherein the hydrothermal reaction conditions in step S3 are as follows: reacting for 8-12 h at 90-120 ℃.
5. The preparation method of the graphene quantum dot/MXene nanosheet two-dimensional composite material according to claim 2, wherein in step S3, the dialysis water washing time is 3-5 d, and the freeze-drying pressure is less than or equal to 200 Pa.
6. The preparation method of the graphene quantum dot/MXene nanosheet two-dimensional composite material according to claim 2, wherein the reaction conditions of etching in step S1 are as follows: reacting for 36-44 h at 25-40 ℃; the concentration of the hydrochloric acid is 8-10 mol/L; the mass ratio of the lithium fluoride to the hydrogen chloride in the hydrochloric acid to the carbon-aluminum-titanium is 1:6.6: 2.
7. The preparation method of the graphene quantum dot/MXene nanosheet two-dimensional composite material according to claim 2, wherein the conditions of centrifugal washing in step S1 are as follows: the centrifugal speed is 4500-7000 rpm, and the supernatant is washed until the pH value is 6-7.
8. The preparation method of the graphene quantum dot/MXene nanosheet two-dimensional composite material according to claim 2, wherein the conditions of the ultrasonic exfoliation in step S1 are as follows: the ultrasonic stripping time is 1-1.5 h, and argon is continuously introduced while ultrasonic treatment is carried out; and carrying out centrifugal screening at the rotating speed of 6000-8000 rpm after the ultrasonic treatment is finished, and freeze-drying the centrifugal supernatant to obtain the single-layer or few-layer MXene nanosheets.
9. The preparation method of the graphene quantum dot/MXene nanosheet two-dimensional composite material according to claim 2, wherein the concentration of the MXene nanosheet dispersion in step S1 is 5-10 g/L.
10. The application of the graphene quantum dot/MXene nanosheet two-dimensional composite material prepared by the preparation method of any one of claims 2 to 9, wherein the graphene quantum dot/MXene nanosheet two-dimensional composite material is used as a hydrogen evolution catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111130565.8A CN113718281B (en) | 2021-09-26 | 2021-09-26 | Graphene quantum dot/MXene nanosheet two-dimensional composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111130565.8A CN113718281B (en) | 2021-09-26 | 2021-09-26 | Graphene quantum dot/MXene nanosheet two-dimensional composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113718281A true CN113718281A (en) | 2021-11-30 |
| CN113718281B CN113718281B (en) | 2023-01-13 |
Family
ID=78684927
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111130565.8A Active CN113718281B (en) | 2021-09-26 | 2021-09-26 | Graphene quantum dot/MXene nanosheet two-dimensional composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113718281B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114464954A (en) * | 2022-01-07 | 2022-05-10 | 大连理工大学 | MXene @ WS for lithium-sulfur battery2Heterostructure material and application thereof |
| CN114460054A (en) * | 2022-01-27 | 2022-05-10 | 江苏省特种设备安全监督检验研究院 | Quantum dot-MXene fluorescence sensor and preparation method and application thereof |
| CN115050586A (en) * | 2022-06-27 | 2022-09-13 | 陕西科技大学 | MXene nanosheet-aspergillus niger carbonized carbon composite material and preparation method and application thereof |
| US20220395822A1 (en) * | 2021-06-15 | 2022-12-15 | Research & Business Foundation Sungkyunkwan University | Mxene nanodot core-carbon shell multifunctional catalyst and method of preparing the same |
| CN115888780A (en) * | 2022-09-30 | 2023-04-04 | 扬州大学 | CuFeS 2 /MXene composite nano material and preparation method thereof |
| CN116328802A (en) * | 2021-12-10 | 2023-06-27 | 华北电力大学（保定） | Preparation method of beta-FeOOH@MXene nanocomposite catalyst |
| CN115050586B (en) * | 2022-06-27 | 2024-04-12 | 陕西科技大学 | MXene nanosheet-aspergillus niger carbonized carbon composite material and preparation method and application thereof |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105576216A (en) * | 2016-03-07 | 2016-05-11 | 浙江理工大学 | Preparation method and application of alpha-nickel sulfide/graphene composite material |
| CN107335451A (en) * | 2017-07-26 | 2017-11-10 | 河海大学 | The preparation method of platinum/molybdenum disulfide nano sheet/graphene three-dimensional combination electrode catalyst |
| CN107938026A (en) * | 2017-11-17 | 2018-04-20 | 浙江大学 | A kind of MXene fibers and preparation method thereof |
| CN109201103A (en) * | 2018-10-17 | 2019-01-15 | 大连理工大学 | A kind of full electrolysis water catalyst of monolithic porous economic benefits and social benefits base metal and synthetic method |
| CN109300701A (en) * | 2018-09-04 | 2019-02-01 | 中山大学 | A kind of efficient electric catalyst composite and its preparation method and application based on hierarchical porous structure graphene aerogel |
| JP2019155349A (en) * | 2018-03-12 | 2019-09-19 | 国立大学法人群馬大学 | Carbon-based composite for oxygen reduction catalyst, and manufacturing and application thereof |
| CN110550632A (en) * | 2019-09-29 | 2019-12-10 | 西南交通大学 | MXene/GO hybrid aerogel microsphere wave absorbing agent and preparation method thereof |
| CN111229273A (en) * | 2020-02-26 | 2020-06-05 | 上海电力大学 | Red phosphorus/black phosphorus heterojunction-Mxene nano electro-catalyst and preparation method thereof |
| CN111471192A (en) * | 2019-10-15 | 2020-07-31 | 中山大学 | Preparation method and application of bismuth tungstate-graphene-conductive hydrogel |
| CN111744519A (en) * | 2020-08-05 | 2020-10-09 | 合肥工业大学 | Preparation method of three-dimensional MXene-based carrier hydrogen evolution catalyst |
| CN111799464A (en) * | 2020-07-08 | 2020-10-20 | 中国科学院电工研究所 | MXene/graphene composite nanosheet, preparation method and application thereof, electrode plate and application thereof |
| CN111790417A (en) * | 2020-05-23 | 2020-10-20 | 同济大学 | Mxene-derived TiO2Nanosheet-graphene gel composite material and preparation method and application thereof |
| CN112133926A (en) * | 2019-06-24 | 2020-12-25 | 河海大学 | Preparation method of platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst |
| CN112151812A (en) * | 2019-06-28 | 2020-12-29 | 河海大学 | Preparation method of rhodium/boron-nitrogen co-doped graphene aerogel three-dimensional composite electrode catalyst |
-
2021
- 2021-09-26 CN CN202111130565.8A patent/CN113718281B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105576216A (en) * | 2016-03-07 | 2016-05-11 | 浙江理工大学 | Preparation method and application of alpha-nickel sulfide/graphene composite material |
| CN107335451A (en) * | 2017-07-26 | 2017-11-10 | 河海大学 | The preparation method of platinum/molybdenum disulfide nano sheet/graphene three-dimensional combination electrode catalyst |
| CN107938026A (en) * | 2017-11-17 | 2018-04-20 | 浙江大学 | A kind of MXene fibers and preparation method thereof |
| JP2019155349A (en) * | 2018-03-12 | 2019-09-19 | 国立大学法人群馬大学 | Carbon-based composite for oxygen reduction catalyst, and manufacturing and application thereof |
| CN109300701A (en) * | 2018-09-04 | 2019-02-01 | 中山大学 | A kind of efficient electric catalyst composite and its preparation method and application based on hierarchical porous structure graphene aerogel |
| CN109201103A (en) * | 2018-10-17 | 2019-01-15 | 大连理工大学 | A kind of full electrolysis water catalyst of monolithic porous economic benefits and social benefits base metal and synthetic method |
| CN112133926A (en) * | 2019-06-24 | 2020-12-25 | 河海大学 | Preparation method of platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst |
| CN112151812A (en) * | 2019-06-28 | 2020-12-29 | 河海大学 | Preparation method of rhodium/boron-nitrogen co-doped graphene aerogel three-dimensional composite electrode catalyst |
| CN110550632A (en) * | 2019-09-29 | 2019-12-10 | 西南交通大学 | MXene/GO hybrid aerogel microsphere wave absorbing agent and preparation method thereof |
| CN111471192A (en) * | 2019-10-15 | 2020-07-31 | 中山大学 | Preparation method and application of bismuth tungstate-graphene-conductive hydrogel |
| CN111229273A (en) * | 2020-02-26 | 2020-06-05 | 上海电力大学 | Red phosphorus/black phosphorus heterojunction-Mxene nano electro-catalyst and preparation method thereof |
| CN111790417A (en) * | 2020-05-23 | 2020-10-20 | 同济大学 | Mxene-derived TiO2Nanosheet-graphene gel composite material and preparation method and application thereof |
| CN111799464A (en) * | 2020-07-08 | 2020-10-20 | 中国科学院电工研究所 | MXene/graphene composite nanosheet, preparation method and application thereof, electrode plate and application thereof |
| CN111744519A (en) * | 2020-08-05 | 2020-10-09 | 合肥工业大学 | Preparation method of three-dimensional MXene-based carrier hydrogen evolution catalyst |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220395822A1 (en) * | 2021-06-15 | 2022-12-15 | Research & Business Foundation Sungkyunkwan University | Mxene nanodot core-carbon shell multifunctional catalyst and method of preparing the same |
| CN116328802A (en) * | 2021-12-10 | 2023-06-27 | 华北电力大学（保定） | Preparation method of beta-FeOOH@MXene nanocomposite catalyst |
| CN116328802B (en) * | 2021-12-10 | 2024-01-30 | 华北电力大学（保定） | Preparation method of beta-FeOOH@MXene nanocomposite catalyst |
| CN114464954A (en) * | 2022-01-07 | 2022-05-10 | 大连理工大学 | MXene @ WS for lithium-sulfur battery2Heterostructure material and application thereof |
| CN114460054A (en) * | 2022-01-27 | 2022-05-10 | 江苏省特种设备安全监督检验研究院 | Quantum dot-MXene fluorescence sensor and preparation method and application thereof |
| CN114460054B (en) * | 2022-01-27 | 2023-05-23 | 江苏省特种设备安全监督检验研究院 | Quantum dot-MXene fluorescent sensor and preparation method and application thereof |
| CN115050586A (en) * | 2022-06-27 | 2022-09-13 | 陕西科技大学 | MXene nanosheet-aspergillus niger carbonized carbon composite material and preparation method and application thereof |
| CN115050586B (en) * | 2022-06-27 | 2024-04-12 | 陕西科技大学 | MXene nanosheet-aspergillus niger carbonized carbon composite material and preparation method and application thereof |
| CN115888780A (en) * | 2022-09-30 | 2023-04-04 | 扬州大学 | CuFeS 2 /MXene composite nano material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113718281B (en) | 2023-01-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113718281B (en) | Graphene quantum dot/MXene nanosheet two-dimensional composite material and preparation method and application thereof | |
| Zhang et al. | Co/MoC nanoparticles embedded in carbon nanoboxes as robust trifunctional electrocatalysts for a Zn–air battery and water electrocatalysis | |
| Zhu et al. | Iridium nanotubes as bifunctional electrocatalysts for oxygen evolution and nitrate reduction reactions | |
| Li et al. | Nitrogen-doped graphitic carbon-supported ultrafine Co nanoparticles as an efficient multifunctional electrocatalyst for HER and rechargeable Zn–air batteries | |
| KR101971260B1 (en) | Preparation Method for Cdot-Pt-Pd Composite, Cdot-Pt-Pd Catalyst thereby and Fuel Cell using the Catalyst | |
| CN108539218B (en) | Electrocatalytic material, preparation method and proton exchange membrane fuel cell | |
| CN110575839B (en) | M2C/carbon nanosheet composite material and preparation method and application thereof | |
| Shi et al. | Biomass-derived precious metal-free porous carbon: Ca-N, P-doped carbon materials and its electrocatalytic properties | |
| Xue et al. | 0D/2D heterojunction of graphene quantum dots/MXene nanosheets for boosted hydrogen evolution reaction | |
| Daryakenari et al. | Highly efficient electrocatalysts fabricated via electrophoretic deposition for alcohol oxidation, oxygen reduction, hydrogen evolution, and oxygen evolution reactions | |
| Qin et al. | MXene supported rhodium nanocrystals for efficient electrocatalysts towards methanol oxidation | |
| CN113279005A (en) | Cobalt doped MoS2/NiS2Preparation method of porous heterostructure material and application of material in electrocatalytic hydrogen evolution | |
| Rahmani et al. | Excellent electro-oxidation of methanol and ethanol in alkaline media: Electrodeposition of the NiMoP metallic nano-particles on/in the ERGO layers/CE | |
| CN111118539A (en) | Nickel-molybdenum oxide quantum dot loaded on nickel oxide nano sheet prepared by electrodeposition method | |
| WO2019158569A1 (en) | Nanomaterial preparation method | |
| CN114318412B (en) | Limited-domain N-doped Fe nano-particles and preparation method and application thereof | |
| CN114045526B (en) | Self-supporting layered double-metal phosphide-graphite alkyne composite catalyst and preparation method and application thereof | |
| CN115896848A (en) | Nitrogen/sulfur co-doped porous carbon loaded zinc monoatomic/metallic copper series catalyst and preparation method and application thereof | |
| Chen et al. | Construction of 3D Hierarchical Co3O4@ CoFe-LDH Heterostructures with Effective Interfacial Charge Redistribution for Rechargeable Liquid/Solid Zn–Air Batteries | |
| CN111359613A (en) | Bifunctional graphene oxide loaded core-shell structure cobalt nanoparticle composite material | |
| Karuppasamy et al. | Rational design and engineering of metal–organic framework-derived trimetallic nicofe-layered double hydroxides as efficient electrocatalysts for water oxidation reaction | |
| CN114164455A (en) | Method for improving electrocatalytic performance of noble metal-based material through electrochemical etching | |
| JP2018528141A (en) | Electrode material for electrolytic hydrogen generation | |
| CN113564629B (en) | Bismuth-based material and preparation method and application thereof | |
| CN114369847A (en) | Iron-nickel alloy @ tungsten carbide/carbon composite catalyst, and preparation method and electrocatalysis application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20221223 Address after: Room 201, floor 2, building 8, No. 29, Huayuan North Road, Haidian District, Beijing 100083 Applicant after: Beijing Sanchuan ENENG Technology Co.,Ltd. Address before: 211100 No. 8 West Buddha Road, Jiangning Development Zone, Jiangsu, Nanjing, China Applicant before: HOHAI University |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |