CN114411191B - Preparation method of high-dispersion graphene oxide supported ruthenium catalyst - Google Patents
Preparation method of high-dispersion graphene oxide supported ruthenium catalyst Download PDFInfo
- Publication number
- CN114411191B CN114411191B CN202111654079.6A CN202111654079A CN114411191B CN 114411191 B CN114411191 B CN 114411191B CN 202111654079 A CN202111654079 A CN 202111654079A CN 114411191 B CN114411191 B CN 114411191B
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- ruthenium
- catalyst
- dispersion
- oxide supported
- 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.)
- Active
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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
-
- 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
-
- 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
-
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
-
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
-
- 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
-
- 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 belongs to the field of electrocatalysis, and relates to a preparation method of a high-dispersion graphene oxide supported ruthenium catalyst. The catalyst is prepared by taking ruthenium particles as an active ingredient, taking graphene oxide as a carrier, dissolving ruthenium metal salt in a solvent, mixing for a certain time, and finally carrying out annealing treatment at a certain temperature. The catalyst has the advantages of high dispersion of active sites, controllable ruthenium carrying capacity, high electrocatalytic hydrogen evolution activity and high stability. The preparation method is simple, the process is environment-friendly and pollution-free, the regulation and control are easy, the yield is high, and the method has a prospect of large-scale commercial application.
Description
Technical Field
The invention relates to the field of electrocatalysis, in particular to a preparation method of a graphene oxide supported ruthenium catalyst with high dispersion and high stability.
Background
The electrochemical decomposition water is used as a pollution-free hydrogen production method with high efficiency, high hydrogen purity, rich reactants (water resources) and large-scale industrial application potential, and the hydrogen production method is widely receivedGeneral attention is paid. However, the rate of hydrogen evolution reaction at the cathode is slow, and there is an urgent need for an efficient and stable catalyst to accelerate the reaction rate and increase the hydrogen production efficiency. Platinum is considered the most effective hydrogen evolution catalyst and then limits its wide range of applications due to its high cost and low yield. Alternatives to platinum are continually being sought to achieve similar performance to platinum at lower cost. Over the past few decades, many non-noble or metal-free catalysts have been developed for hydrogen evolution reactions, but their lower activity and stability still fall short of the requirements for substituted platinum-based catalysts. Since ruthenium and platinum have similar hydrogen bond strength (-65 kcal mol) -1 ) Is considered as a potential hydrogen evolution reaction catalyst. Notably, the price of ruthenium has a major advantage among the many noble metals, being only 1/4 of that of platinum, for which ruthenium-based HER catalysts are widely studied and are expected to be platinum-substituted HER catalysts.
The prior art is studied, firstly gold nano-wires are used as a sacrificial template, then a layer of ultrathin ruthenium shell is coated, finally the gold nano-wires are etched in dimethylformamide by copper ions, and a tubular face-centered cubic ruthenium nano-catalyst is formed, wherein the wall thickness of the tubular face-centered cubic ruthenium nano-catalyst is only 5 to 9 atomic layers. Because of its unique structure, the material shows higher catalytic activity under alkaline conditions, but does not fundamentally solve the problem of rare noble metals, and has complex synthesis process and lower yield. There is also studied a method of preparing a carbon nanotube-supported ruthenium nanoparticle catalyst by treating a multiwall carbon nanotube with nitric acid first, then reducing ruthenium on the carbon nanotube in the presence of sodium borohydride, and finally performing annealing heat treatment. The catalyst shows activity and stability exceeding those of commercial platinum carbon catalysts under a three-electrode test system, but the synthesis process can pollute the environment and is not practically applied in an electrolytic tank. The preparation method of the supported ruthenium catalyst disclosed in the prior art still has a plurality of defects, such as complex preparation process, large noble metal precursor dosage, small loading capacity and lack of research on the stability and dispersibility of the catalyst material.
Although the current ruthenium-based hydrogen evolution catalyst has great potential, the existing catalyst preparation process still has the problems of large environmental pollution, low noble metal utilization rate, poor catalyst activity and stability, and the like, and is not beneficial to large-scale industrial production. Therefore, development of a ruthenium-based catalyst which has simple manufacturing process, no pollution and little waste in the production process and is applicable to mass production and can replace platinum-based catalysts and has high activity and high stability is imperative.
Disclosure of Invention
Accordingly, the present invention aims to provide a preparation method of graphene oxide supported ruthenium catalyst with high dispersion and high stability, which can be scaled up in large scale to solve the above problems.
The technical scheme of the invention is realized as follows: the preparation method of the high-dispersion graphene oxide supported ruthenium catalyst comprises the following steps:
(1) Preparation of ruthenium metal precursor solution: dissolving ruthenium metal salt in a first solvent, and uniformly mixing to obtain ruthenium metal precursor solution; the concentration range of the ruthenium metal salt in the ruthenium metal precursor solution is 1-20 mg/mL; the concentration is too high, the probability of ruthenium agglomeration into large particles is increased, the quality activity is reduced, and the performance is not facilitated; the concentration is too low, the load capacity is insufficient, and the performance is reduced.
(2) Preparation of graphene oxide solution: dissolving graphene oxide in a second solvent, and uniformly mixing to obtain a graphene oxide solution; the concentration range of the graphene oxide in the graphene oxide solution is 0.05-5 mg/mL; the concentration is too low to provide enough loading space for ruthenium metal, too high, and the relative loading is reduced.
(3) Preparing a high-dispersion graphene oxide supported ruthenium precursor: adding the ruthenium metal precursor solution into the graphene oxide solution, uniformly mixing, centrifuging to obtain gel, and drying the gel to obtain a high-dispersion graphene oxide supported ruthenium precursor; the volume ratio of the ruthenium metal precursor solution to the graphene oxide solution is 0.02-0.04; this step requires centrifugation to obtain a gel state.
(4) Preparation of a high-dispersion graphene oxide supported ruthenium catalyst: and (3) carrying out heat treatment on the high-dispersion graphene oxide supported ruthenium precursor under the inert gas atmosphere, wherein the gas flow rate is 10-150 mL/min, heating to 500-900 ℃ at the speed of 5-15 ℃/min for heat preservation, and preferably, the heat preservation time is 0.5-5 h, and cooling to obtain the high-dispersion graphene oxide supported ruthenium catalyst. The ruthenium metal salt is added into the graphene oxide to form graphene gel, the generated cross-linking structure is beneficial to fixing ruthenium metal ions, and the heating speed cannot be too slow in the heat treatment process, but is not enough to form a target catalyst with high dispersion, high loading, high catalytic performance and high stability, if the heating speed is more than or equal to 5 ℃/min.
Preferably, the ruthenium metal salt in the step (1) is ruthenium trichloride trihydrate, ruthenium acetylacetonate or ruthenium acetate.
Preferably, the first solvent in the step (1) is deionized water, alcohols, a mixture of alcohols and water, or a mixture of alcohols and acetone. For example, the alcohol may be ethanol, methanol, isopropanol, or the like.
Preferably, the mixing method in the step (1) is magnetic stirring or ultrasonic, and the time is 0.5-1 h.
Preferably, the second solvent in the step (2) is deionized water, alcohols, a mixture of alcohols and water, or a mixture of alcohols and acetone.
Preferably, the second solvent in step (2) and the first solvent in step (1) are the same solvent.
Preferably, the mixing method in the step (2) is magnetic stirring or ultrasonic for 2-5 hours. The time cannot be too short, and graphene oxide needs a certain amount of ultrasound for a long time to be dispersed sufficiently, and the ultrasound is insufficient for two hours, so that the dispersion is incomplete.
Preferably, the mixing method in the step (3) is magnetic stirring or ultrasonic, and the time is 0.5-2 h. If the time is too short, the ruthenium metal salt precursor is unevenly dispersed.
Preferably, in the step (3), the ruthenium metal precursor solution is added into the graphene oxide solution, uniformly mixed and centrifuged for 5-10 min at the rotating speed of 8000-12000 rpm to obtain gel.
Preferably, in the step (3), the gel is dried in a vacuum environment at 50-80 ℃ to obtain the high-dispersion graphene oxide supported ruthenium precursor. It must be vacuum dried, otherwise the material will collapse drastically due to water loss.
Compared with the prior art, the invention has the beneficial effects that:
(1) Compared with the prior art, the preparation method of the graphene oxide supported ruthenium catalyst with high dispersion and high stability is simpler and more convenient, the synthesis process only involves two solid raw materials and two or one solvent, the synthesis process is environment-friendly, no polluted waste liquid is generated, and the ruthenium salt utilization rate is high;
(2) The method provided by the invention can directly expand the multiple to realize the large-scale production and preparation of the catalyst, and can effectively reduce the industrialization cost of the catalyst;
(3) The graphene oxide supported ruthenium catalyst provided by the invention has the characteristic of high dispersion of active sites. By the thermal annealing treatment, the internal stress of the material which is compressed during vacuum drying is eliminated, and ruthenium is reduced to small particles on the surface of the carrier and has a strong interaction with the carrier. The average grain diameter of the ruthenium nano particles is about 2nm, and the ruthenium nano particles are uniformly distributed on the surface of the two-dimensional graphene oxide, so that the prepared catalyst has higher stability and corrosion resistance through strong interaction generated by bonding between ruthenium and carbon.
(4) The catalyst prepared by the invention has higher catalytic performance for cathodic hydrogen precipitation reaction, and the catalyst has the catalytic performance of 1A mg -1 The mass activity is 1-4 times of that of the commercial Pt/C catalyst, and the catalyst has good stability.
Drawings
Fig. 1 is a TEM image of the high dispersion graphene oxide supported ruthenium catalyst prepared in example 1.
Fig. 2 is an XRD pattern of the high dispersion graphene oxide supported ruthenium catalyst prepared in example 1.
FIG. 3 is a graph showing polarization of hydrogen evolution at room temperature, 1M KOH, for the highly dispersed graphene oxide supported ruthenium catalyst and commercial platinum/carbon catalyst prepared in example 1.
FIG. 4 is a graph showing polarization of hydrogen evolution after 5 ten thousand cycles of accelerated durability test in 1M KOH for the high dispersion graphene oxide supported ruthenium catalyst and commercial platinum/carbon catalyst prepared in example 1.
Detailed Description
In order to better understand the technical content of the present invention, the following provides specific examples to further illustrate the present invention.
The experimental methods used in the embodiment of the invention are conventional methods unless otherwise specified. Materials, reagents, and the like used in the examples of the present invention are commercially available unless otherwise specified.
Example 1: high-dispersion graphene oxide supported ruthenium catalyst
(1) Preparation of ruthenium metal precursor solution
17mg of ruthenium trichloride trihydrate is placed in a beaker, 1.7mL of deionized water is added, and ultrasound is performed for 30min, so as to obtain a ruthenium metal precursor solution.
(2) Preparation of graphene oxide solution
100mg of graphene oxide is placed in a beaker, 70mL of deionized water is added, and ultrasonic treatment is performed for 2 hours, so that a graphene oxide solution is obtained.
(3) Preparation of high-dispersion graphene oxide supported ruthenium precursor
Adding the ruthenium metal precursor solution prepared in the step (1) into the graphene oxide solution prepared in the step (2), wherein the volume ratio of the ruthenium metal precursor solution to the graphene oxide solution is 0.024, magnetically stirring for 1h, centrifuging the mixed solution at the rotating speed of 9000rpm for 5min to obtain black gel, collecting the black gel, placing into a vacuum drying oven, and drying at 70 ℃ for 24h to obtain the high-dispersion graphene oxide supported ruthenium precursor.
(4) Preparation of high-dispersion graphene oxide supported ruthenium catalyst
Grinding the high-dispersion graphene oxide supported ruthenium precursor prepared in the step (3), then placing the ground high-dispersion graphene oxide supported ruthenium precursor into a quartz boat, placing the quartz boat into a tube furnace, heating to 700 ℃ at a heating rate of 10 ℃/min under an argon flow rate of 30mL/min, and preserving heat for 2 hours, and obtaining the high-dispersion graphene oxide supported ruthenium catalyst after natural cooling.
(5) Structural morphology characterization and performance test of catalyst
(A) Structural morphology and elemental characterization of the catalyst:
an image (fig. 1) of the highly dispersed graphene oxide supported ruthenium catalyst was observed by a Transmission Electron Microscope (TEM), and the ruthenium particle size of the highly dispersed graphene oxide supported ruthenium catalyst prepared in this example was in the range of 1.5 to 2.5nm. And it is apparent from the figure that the prepared catalyst material exhibits a uniform particle distribution structure.
The elemental composition information of the highly dispersed graphene oxide supported ruthenium catalyst was characterized by X-ray diffraction (XRD) (fig. 2). As can be seen from fig. 2, the prepared material exhibits relatively obvious XRD diffraction peak information of ruthenium element.
(B) Cathode hydrogen evolution catalytic performance test:
the hydrogen evolution activity of the catalyst was measured by linear scanning at a sweep rate of 2mV/s in 1MKOH at 0V to-0.3V (vs RHE) using a three electrode system, and the results are shown in FIG. 3.
The three-electrode system is adopted, the cyclic scanning is carried out in 1MKOH at a scanning speed of 100mV/s under the condition of 0.05V to-0.15V (vs RHE), and the polarization curve of hydrogen precipitation after 5 ten thousand circles is shown in figure 4. As can be seen from fig. 4, the catalyst performance remained good with little decay after a long period of accelerated aging testing.
The catalyst prepared in this example was 1A mg -1 The hydrogen evolution mass activity at this point was 3.2 times that of commercial platinum/carbon, with a ruthenium loading of 7.6wt% as measured by Inductively Coupled Plasma (ICP).
The catalyst according to the present invention was identical to the above test methods for cathodic hydrogen evolution and catalyst stability test methods, except for the specific description.
Example 2: experiment of 5-fold magnification of raw materials and solvent
(1) Preparation of ruthenium metal precursor solution
85mg of ruthenium trichloride trihydrate is placed in a beaker, 8.5mL of deionized water is added, and ultrasound is performed for 30min, so as to obtain a ruthenium metal precursor solution.
(2) Preparation of graphene oxide solution
500mg of graphene oxide is put into a beaker, 350mL of deionized water is added, and ultrasonic treatment is carried out for 2 hours, so as to obtain a graphene oxide solution
(3) Preparation of high-dispersion graphene oxide supported ruthenium precursor
Adding the ruthenium metal precursor solution prepared in the step (1) into the graphene oxide solution in the step (2), wherein the volume ratio of the ruthenium metal precursor solution to the graphene oxide solution is 0.024, magnetically stirring for 1h, centrifuging the mixed solution at the rotating speed of 9000rpm for 5min, collecting black gel, placing into a vacuum drying oven, and drying at 70 ℃ for 48h to obtain the high-dispersion graphene oxide supported ruthenium precursor.
(4) Preparation of high-dispersion graphene oxide supported ruthenium catalyst
Grinding the high-dispersion graphene oxide supported ruthenium precursor prepared in the step (3), then placing the ground high-dispersion graphene oxide supported ruthenium precursor into a quartz boat, heating to 700 ℃ at a heating rate of 10 ℃/min under an argon flow rate of 30mL/min, and preserving heat for 2 hours, and obtaining the high-dispersion graphene oxide supported ruthenium catalyst after natural cooling.
(5) Structural morphology characterization and performance test of catalyst
The appearance and performance test method of the catalyst are completely the same as those of the embodiment 1, the particle size range of ruthenium particles of the high-dispersion graphene oxide supported ruthenium catalyst prepared by the embodiment is 1.5-2.5nm, the prepared catalyst material presents a uniform particle distribution structure, the hydrogen precipitation performance of the catalyst prepared by the embodiment is basically consistent with that of the embodiment 1, and the catalyst is 1A mg -1 The hydrogen evolution mass activity at this point was 3.2 times that of the commercial platinum/carbon catalyst, with a ruthenium loading of 7.5wt%.
Example 3: experiment of raw materials and solvents amplified 10 times
This embodiment differs from embodiment 1 in that,
step (1) preparation of ruthenium Metal precursor solution
170mg of ruthenium trichloride trihydrate is placed in a beaker, 17mL of deionized water is added, and ultrasound is performed for 30min, so as to obtain a ruthenium metal precursor solution.
Preparation of graphene oxide solution in step (2)
1000mg of graphene oxide is placed in a beaker, 700mL of deionized water is added, and ultrasonic treatment is performed for 2 hours, so that a graphene oxide solution is obtained.
The remaining steps and conditions were the same as in example 1. The grain diameter range of ruthenium particles of the prepared high-dispersion graphene oxide supported ruthenium catalyst is 1.5-2.5nm, and the prepared catalyst material still presents a uniform grain distribution structure, which is 1A mg -1 The hydrogen evolution mass activity at this point was 3.2 times that of the commercial platinum/carbon catalyst, with a ruthenium loading of 7.5wt%.
Example 4: high-dispersion graphene oxide supported ruthenium catalyst
This example is different from example 1 in that the heat treatment temperature in step (4) is 500℃and the heat treatment process and other steps are carried out for 2 hours, and the preparation process and test method are exactly the same as those in example 1. The particle size range of ruthenium particles of the high-dispersion graphene oxide supported ruthenium catalyst prepared in the embodiment is 1.5-2.5nm, the prepared catalyst material shows a uniform particle distribution structure, and the catalyst prepared in the embodiment is 1A mg -1 The hydrogen evolution mass activity at this point was 1.8 times that of a commercial platinum/carbon catalyst, and the ruthenium loading was 11.6wt% as measured by Inductively Coupled Plasma (ICP).
Example 5: high-dispersion graphene oxide supported ruthenium catalyst
This example differs from example 1 in that the heat treatment temperature in step (4) was 900℃for 2 hours, and the heat treatment process and other steps were identical to those of example 1. The particle size range of ruthenium particles of the high-dispersion graphene oxide supported ruthenium catalyst prepared in the embodiment is 1.5-2.5nm, the prepared catalyst material shows a uniform particle distribution structure, and the catalyst prepared in the embodiment is 1A mg -1 The hydrogen evolution mass activity at this point was 3.5 times that of commercial platinum carbon, with a ruthenium loading of 5.9wt% as measured by Inductively Coupled Plasma (ICP).
Example 6: high-dispersion graphene oxide supported ruthenium catalyst
(1) Preparation of ruthenium metal precursor solution
10mg of ruthenium acetate was placed in a beaker, 10mL of ethanol was added, and the mixture was magnetically stirred for 1 hour to obtain a ruthenium metal precursor solution.
(2) Preparation of graphene oxide solution
100mg of graphene oxide is placed in a beaker, 2000mL of ethanol is added, and the mixture is magnetically stirred for 5 hours to obtain a graphene oxide solution.
(3) Preparation of high-dispersion graphene oxide supported ruthenium precursor
Adding the ruthenium metal precursor solution prepared in the step (1) into the graphene oxide solution prepared in the step (2), wherein the volume ratio of the ruthenium metal precursor solution to the graphene oxide solution is 0.04, carrying out ultrasonic treatment for 30min, centrifuging the mixed solution at the rotating speed of 9000rpm for 5min to obtain black gel, collecting the black gel, placing the black gel into a vacuum drying oven, and drying at 50 ℃ for 24h to obtain the high-dispersion graphene oxide supported ruthenium precursor.
(4) Preparation of high-dispersion graphene oxide supported ruthenium catalyst
Grinding the high-dispersion graphene oxide supported ruthenium precursor prepared in the step (3), then placing the ground high-dispersion graphene oxide supported ruthenium precursor into a quartz boat, placing the quartz boat into a tube furnace, heating to 900 ℃ at a heating rate of 5 ℃/min under an argon flow rate of 150mL/min, and preserving heat for 30min, and obtaining the high-dispersion graphene oxide supported ruthenium catalyst after natural cooling.
The particle size of ruthenium particles of the high-dispersion graphene oxide supported ruthenium catalyst prepared in the embodiment ranges from 1.5 nm to 2.5nm, the prepared catalyst material shows a uniform particle distribution structure, and the catalyst prepared in the embodiment is 1Amg -1 The hydrogen evolution mass activity at this point was 3.3 times that of commercial platinum carbon, with a ruthenium loading of 6.9wt% as measured by Inductively Coupled Plasma (ICP).
Example 7: high-dispersion graphene oxide supported ruthenium catalyst
(1) Preparation of ruthenium metal precursor solution
20mg of ruthenium acetylacetonate is placed in a beaker, 1mL of ethanol is added, and the mixture is subjected to ultrasonic treatment for 30min to obtain a ruthenium metal precursor solution.
(2) Preparation of graphene oxide solution
100mg of graphene oxide is placed in a beaker, 20mL of ethanol is added, and the ultrasonic treatment is carried out for 2 hours, so that a graphene oxide solution is obtained.
(3) Preparation of high-dispersion graphene oxide supported ruthenium precursor
Adding the ruthenium metal precursor solution prepared in the step (1) into the graphene oxide solution prepared in the step (2), wherein the volume ratio of the ruthenium metal precursor solution to the graphene oxide solution is 0.04, carrying out ultrasonic treatment for 30min, centrifuging the mixed solution at the rotating speed of 9000rpm for 5min to obtain black gel, collecting the black gel, placing the black gel into a vacuum drying oven, and drying at 80 ℃ for 24h to obtain the high-dispersion graphene oxide supported ruthenium precursor.
(4) Preparation of high-dispersion graphene oxide supported ruthenium catalyst
Grinding the high-dispersion graphene oxide supported ruthenium precursor prepared in the step (3), then placing the ground high-dispersion graphene oxide supported ruthenium precursor into a quartz boat, placing the quartz boat into a tube furnace, heating to 500 ℃ at a heating rate of 15 ℃/min under an argon flow rate of 10mL/min, and preserving heat for 5 hours, and obtaining the high-dispersion graphene oxide supported ruthenium catalyst after natural cooling.
The particle size of ruthenium particles of the high-dispersion graphene oxide supported ruthenium catalyst prepared in the embodiment ranges from 1.5 nm to 2.5nm, the prepared catalyst material shows a uniform particle distribution structure, and the catalyst prepared in the embodiment is 1Amg -1 The hydrogen evolution mass activity at this point was 3.5 times that of commercial platinum carbon, with a ruthenium loading of 5.2wt% as measured by Inductively Coupled Plasma (ICP).
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (4)
1. The preparation method of the high-dispersion graphene oxide supported ruthenium catalyst is characterized by comprising the following steps of:
(1) Preparation of ruthenium metal precursor solution: dissolving ruthenium metal salt in a first solvent, wherein the first solvent is deionized water or ethanol, and uniformly mixing to obtain ruthenium metal precursor solution; the concentration range of the ruthenium metal salt in the ruthenium metal precursor solution is 1-20 mg/mL;
(2) Preparation of graphene oxide solution: dissolving graphene oxide in a second solvent, wherein the second solvent is deionized water or ethanol; magnetically stirring or ultrasonic treatment is carried out for 2-5 hours, and graphene oxide solution is obtained after uniform mixing; the concentration range of the graphene oxide in the graphene oxide solution is 0.05-5 mg/mL;
(3) Preparing a high-dispersion graphene oxide supported ruthenium precursor: adding the ruthenium metal precursor solution into the graphene oxide solution, magnetically stirring or carrying out ultrasonic treatment for 0.5-2 hours, uniformly mixing, centrifuging for 5-10 minutes at the rotating speed of 8000-12000 rpm to obtain gel, and drying the gel in a vacuum environment at 50-80 ℃ to obtain a high-dispersion graphene oxide supported ruthenium precursor; the volume ratio of the ruthenium metal precursor solution to the graphene oxide solution is 0.02-0.04;
(4) Preparation of a high-dispersion graphene oxide supported ruthenium catalyst: and (3) carrying out heat treatment on the high-dispersion graphene oxide supported ruthenium precursor in an inert gas atmosphere, wherein the gas flow rate is 10-150 mL/min, heating to 500-900 ℃ at a rate of 5-15 ℃/min, carrying out heat preservation, and cooling to obtain the high-dispersion graphene oxide supported ruthenium catalyst.
2. The method for preparing a high-dispersion graphene oxide supported ruthenium catalyst according to claim 1, wherein the ruthenium metal salt in the step (1) is ruthenium trichloride trihydrate, ruthenium acetylacetonate or ruthenium acetate.
3. The method for preparing the high-dispersion graphene oxide supported ruthenium catalyst according to claim 1, wherein the mixing method in the step (1) is magnetic stirring or ultrasonic, and the time is 0.5-1 h.
4. The method for preparing a highly dispersed graphene oxide supported ruthenium catalyst according to claim 1, wherein the second solvent in the step (2) and the first solvent in the step (1) are the same solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111654079.6A CN114411191B (en) | 2021-12-30 | 2021-12-30 | Preparation method of high-dispersion graphene oxide supported ruthenium catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111654079.6A CN114411191B (en) | 2021-12-30 | 2021-12-30 | Preparation method of high-dispersion graphene oxide supported ruthenium catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114411191A CN114411191A (en) | 2022-04-29 |
| CN114411191B true CN114411191B (en) | 2023-04-25 |
Family
ID=81269340
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111654079.6A Active CN114411191B (en) | 2021-12-30 | 2021-12-30 | Preparation method of high-dispersion graphene oxide supported ruthenium catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114411191B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109603819A (en) * | 2018-12-11 | 2019-04-12 | 山西大学 | A kind of graphene-supported PdRu bimetallic catalyst and its preparation method and application |
| CN110813282A (en) * | 2019-09-27 | 2020-02-21 | 南京宁智高新材料研究院有限公司 | Device and method for coupling application of single-site metal catalyst and electrolytic hydrogen sulfide system |
| CN111068717A (en) * | 2019-12-10 | 2020-04-28 | 西北大学 | Ruthenium simple substance modified sulfur-doped graphene two-dimensional material and preparation and application thereof |
| CN111939940A (en) * | 2020-07-03 | 2020-11-17 | 南方科技大学 | Ruthenium-based catalyst and preparation method and application thereof |
| CN112877725A (en) * | 2021-01-12 | 2021-06-01 | 河南工业大学 | Ruthenium/ruthenium oxide modified nitrogen-doped graphene three-dimensional composite material and preparation method and application thereof |
-
2021
- 2021-12-30 CN CN202111654079.6A patent/CN114411191B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109603819A (en) * | 2018-12-11 | 2019-04-12 | 山西大学 | A kind of graphene-supported PdRu bimetallic catalyst and its preparation method and application |
| CN110813282A (en) * | 2019-09-27 | 2020-02-21 | 南京宁智高新材料研究院有限公司 | Device and method for coupling application of single-site metal catalyst and electrolytic hydrogen sulfide system |
| CN111068717A (en) * | 2019-12-10 | 2020-04-28 | 西北大学 | Ruthenium simple substance modified sulfur-doped graphene two-dimensional material and preparation and application thereof |
| CN111939940A (en) * | 2020-07-03 | 2020-11-17 | 南方科技大学 | Ruthenium-based catalyst and preparation method and application thereof |
| CN112877725A (en) * | 2021-01-12 | 2021-06-01 | 河南工业大学 | Ruthenium/ruthenium oxide modified nitrogen-doped graphene three-dimensional composite material and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| Seo-Yoon Bae et al..Recent advances in ruthenium-based electrocatalysts for the hydrogen evolution reaction.Nanoscale Horizons.2019,第43-56页. * |
| Yang Li et al..Implanting Ru nanoclusters into N-doped graphene for efficient alkaline hydrogen evolution.Carbon.2021,第362-367页. * |
| Yingjie Yang et al..Bridge the activity and durability of Ruthenium for hydrogen evolution reaction with the Ru–O–C link.Chemical Engineering Journal.2021,第1-7页. * |
| 倪军 等.新型碳材料在催化领域中的应用及进展.分子催化.2016,30(3),第282-296页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114411191A (en) | 2022-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113600209B (en) | Method for preparing high-dispersion carbon-supported Pt-based ordered alloy catalyst and catalyst | |
| CN111509236A (en) | One-dimensional porous platinum-containing alloy nanowire catalyst and preparation method thereof | |
| CN112103520B (en) | Anode catalyst of alcohol fuel cell | |
| CN110961162B (en) | Catalyst carrier, precious metal catalyst, and preparation method and application thereof | |
| CN104307512A (en) | Supported palladium catalyst and preparation method and application thereof | |
| CN111584889A (en) | Zinc-containing monatomic catalyst and preparation method and application thereof | |
| CN110581281B (en) | PdCu alloy nano catalyst applied to fuel cell field and preparation method thereof | |
| CN111244484B (en) | Preparation method of sub-nano platinum-based ordered alloy | |
| CN111921551A (en) | Preparation method of nitrogen-doped carbon frame material coated with iron-cobalt-nickel ternary alloy | |
| CN111430733B (en) | Non-noble metal oxygen reduction catalyst for fuel cell and preparation method thereof | |
| CN109499602B (en) | Synthesis method for systematically regulating and controlling number of atoms of load type iron atom cluster | |
| CN110767915A (en) | Silver-manganese bimetallic composite catalyst for oxygen reduction reaction in alkaline medium and synthesis method thereof | |
| CN114345324A (en) | Biomass carbon-based metal single-atom composite catalyst, preparation method and application thereof | |
| CN111346645B (en) | Preparation method and application of high-dispersion alloy nano particles | |
| CN115570143B (en) | Low-platinum high-entropy alloy nano-particle and preparation method and application thereof | |
| CN114411191B (en) | Preparation method of high-dispersion graphene oxide supported ruthenium catalyst | |
| CN107369839B (en) | preparation method of ruthenium oxide-diatomite composite supported fuel cell catalyst | |
| CN114530608B (en) | Catalyst for fuel cell, preparation method of catalyst and fuel cell | |
| CN114497603B (en) | Catalyst for fuel cell, preparation method of catalyst and fuel cell | |
| CN112871215B (en) | Preparation method and application of iron-doped cobalt imidazolide hollow nano catalytic material | |
| CN114497587B (en) | Catalyst in proton exchange membrane fuel cell and preparation method thereof | |
| CN114566662A (en) | High-entropy intermetallic compound with ordered structure, preparation method thereof and application of intermetallic compound as fuel cell cathode catalyst | |
| CN114256470A (en) | Cobalt-iron alloy nano-particles based on hollow cubic carbon material and preparation method and application thereof | |
| CN114284513A (en) | Preparation method of nitrogen-doped graphite mono-alkyne supported noble metal nanoparticle electrocatalyst | |
| CN109280800B (en) | Series PdxSny alloy nanocrystals and preparation method and 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |