CN113522277A - Ruthenium dioxide/graphene two-dimensional material, and preparation method and application thereof - Google Patents
Ruthenium dioxide/graphene two-dimensional material, and preparation method and application thereof Download PDFInfo
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- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 title claims abstract description 236
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 131
- 239000000463 material Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000001301 oxygen Substances 0.000 claims abstract description 34
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 34
- 230000007547 defect Effects 0.000 claims abstract description 22
- 229910052707 ruthenium Inorganic materials 0.000 claims description 34
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 33
- 239000002243 precursor Substances 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000000137 annealing Methods 0.000 claims description 18
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 238000004108 freeze drying Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000010411 electrocatalyst Substances 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000011261 inert gas Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 11
- GZLCNRXKVBAALW-UHFFFAOYSA-N O=[Ru](=O)=O Chemical compound O=[Ru](=O)=O GZLCNRXKVBAALW-UHFFFAOYSA-N 0.000 abstract description 3
- 229910002804 graphite Inorganic materials 0.000 abstract 1
- 239000010439 graphite Substances 0.000 abstract 1
- -1 graphite alkene Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 29
- 230000002950 deficient Effects 0.000 description 15
- 239000003792 electrolyte Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000007710 freezing Methods 0.000 description 5
- 230000008014 freezing Effects 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 239000012670 alkaline solution Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
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- 238000001179 sorption measurement Methods 0.000 description 4
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- 238000005260 corrosion Methods 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005247 gettering Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
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- C01G55/004—Oxides; Hydroxides
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- Y02E60/30—Hydrogen technology
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Abstract
The application discloses ruthenium dioxide/graphite alkene two-dimensional material includes: graphene; ruthenium dioxide adsorbed on the graphene; wherein the ruthenium dioxide/graphene two-dimensional material has intrinsic defects. The application also provides a preparation method and application of the ruthenium dioxide/graphene two-dimensional material. The ruthenium dioxide/graphene two-dimensional material has an intrinsic oxygen defect ruthenium dioxide structure, does not need to be corroded by an acid solution, and effectively solves the problem that the ruthenium dioxide oxygen defect structure can only be generated in the acid solution.
Description
Technical Field
The application relates to a ruthenium dioxide/graphene two-dimensional material, a preparation method and application thereof, and belongs to the field of materials.
Background
The development of efficient oxygen evolution electrocatalysts is the key to electrochemical water splitting and regenerative fuel cells. Oxygen evolution powerThe catalyst typically operates in corrosive solutions, including acidic and alkaline electrolytes. So far, only Ir and Ru oxygen evolution electrocatalysts can stably work in various electrolytes. Particularly, the ruthenium dioxide-based electrocatalyst is considered to be the best oxygen evolution electrocatalyst in the acidic electrolyte, and recently, the Zhongming research group of the national research center of combined-fertilizer micro-scale material science of the university of Chinese science and technology cooperates with the Huzheng 33411of southern university, so that the electrolyzed water catalyst which is efficient and stable under the acidic condition is developed by constructing the composite ruthenium-based oxide, and the polarization current of the composite ruthenium-based oxide reaches 10mAcm-2The current density of (A) only needs over potential of 171mV, which is the lowest value reported in the related field at present. Principle of excellent acidic oxygen evolution electrocatalytic activity of ruthenium dioxide transition metal elements in the ruthenium dioxide-based complex compounds are leached out by acid corrosion, resulting in the appearance of Ru sites with oxygen unsaturation, which become high-activity catalytic sites. This defective structure leads to an increase in the oxygen evolution activity of ruthenium dioxide. However, such a defective structure is rarely formed when ruthenium dioxide is operated in an alkaline solution, because the transition metal element of the composite ruthenium-based oxide is hardly dissolved and precipitated in an alkaline electrolyte. Thus, ruthenium dioxide requires an overpotential of 240mV in alkaline electrolyte to reach 10mAcm-2The polarization current density of (a) far behind the optimal alkaline oxygen evolution electrocatalyst (190mV overpotential, up to 10mAcm "2), hinders the application of ruthenium dioxide in alkaline electrocatalysis. In conclusion, the existing ruthenium dioxide can only work efficiently in an acid electrolyte, and has low working efficiency in an alkaline electrolyte. However, the existing preparation method can not prepare the ruthenium dioxide with the intrinsic defect structure. Therefore, the development of a ruthenium dioxide structure with an intrinsic defect structure that does not require corrosion is an ideal approach to the development of oxygen evolution catalysts that are ultra-high activity and capable of working in different electrolytes.
Disclosure of Invention
According to the first aspect of the application, the ruthenium dioxide/graphene two-dimensional material is provided, the ruthenium dioxide/graphene two-dimensional material has an intrinsic oxygen defect ruthenium dioxide structure, and the problem that the ruthenium dioxide oxygen defect structure can only be generated in an acid solution is effectively solved without being corroded by the acid solution.
The ruthenium dioxide/graphene two-dimensional material comprises: graphene; ruthenium dioxide adsorbed on the graphene; wherein the ruthenium dioxide/graphene two-dimensional material has intrinsic defects.
Optionally, the thickness of the ruthenium dioxide/graphene two-dimensional material is 1-20 nm.
Optionally, the thickness of the ruthenium dioxide/graphene two-dimensional material is 1-9 nm.
Optionally, the specific surface area of the ruthenium dioxide/graphene two-dimensional material is 50-300 m2 g-1。
Optionally, the specific surface area of the ruthenium dioxide/graphene two-dimensional material is 125-300 m2 g-1。
Optionally, the coordination number of Ru in the ruthenium dioxide/graphene two-dimensional material is less than 6.
Optionally, the ruthenium dioxide/graphene two-dimensional material is a two-dimensional heterostructure of ruthenium dioxide and graphene.
Optionally, the mass ratio of the graphene to the ruthenium dioxide in the ruthenium dioxide/graphene two-dimensional material is 5-95: 100.
Optionally, the mass ratio of the graphene to the ruthenium dioxide in the ruthenium dioxide/graphene two-dimensional material is 5:100, 10:100, 15:100, 20:100, 25:100, 30:100, 35:100, 40:100, 45:100, 50:100, 55:100, 60:100, 65:100, 70:100, 75:100, 80:100, 85:100, 90:100, 95: 100.
According to a second aspect of the present application, there is provided a method for preparing a ruthenium dioxide/graphene two-dimensional material, comprising: a) preparing a solution containing a ruthenium precursor and graphene oxide; b) drying the solution; and c) annealing the solid dried in the step b) in the presence of inactive gas to obtain the ruthenium dioxide/graphene two-dimensional material.
Optionally, the ruthenium precursor is selected from ruthenium trichloride or ruthenium trichloride hydrate.
Optionally, the step a) comprises: respectively preparing a graphene oxide dispersion liquid and a solution containing a ruthenium precursor; and adding the solution containing the ruthenium precursor into the graphene oxide dispersion liquid and uniformly mixing.
Optionally, the solvent of the graphene oxide dispersion liquid is water, and the concentration of the solvent is 0.5-5 g/L; the solvent of the solution containing the ruthenium precursor is water, and the concentration of the solvent is 10-100 g/L.
Optionally, the upper limit of the concentration of the graphene oxide dispersion is selected from 1g/L, 1.5g/L, 2g/L, 2.5g/L, 3g/L, 3.5g/L, 4g/L, 4.5g/L, or 5 g/L.
Optionally, the lower limit of the concentration of the graphene oxide dispersion is selected from 0.5g/L, 1g/L, 1.5g/L, 2g/L, 2.5g/L, 3g/L, 3.5g/L, 4g/L, or 4.5 g/L.
Optionally, the upper limit of the concentration of the ruthenium precursor-containing solution is selected from 15g/L, 20g/L, 25g/L, 30g/L, 35g/L, 40g/L, 45g/L, 50g/L, 55g/L, 60g/L, 65g/L, 70g/L, 75g/L, 80g/L, 85g/L, 90g/L, 95g/L, or 100 g/L.
Optionally, the lower limit of the concentration of the ruthenium precursor-containing solution is selected from 10g/L, 15g/L, 20g/L, 25g/L, 30g/L, 35g/L, 40g/L, 45g/L, 50g/L, 55g/L, 60g/L, 65g/L, 70g/L, 75g/L, 80g/L, 85g/L, 90g/L, or 95 g/L.
Optionally, the concentration of the graphene oxide dispersion liquid is 1 g/L; the concentration of the solution containing the ruthenium precursor was 20 g/L.
Optionally, in the step a), the mass ratio of the ruthenium precursor to the graphene oxide is 0.1-10: 1.
Optionally, in the step a), the mass ratio of the ruthenium precursor to the graphene oxide is 0.1:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10: 1.
Preferably, in step a), the mass ratio of the ruthenium precursor to the graphene oxide is 0.5: 1.
Optionally, the adding is dropwise adding, and the dropwise adding time is 5-20 minutes; the uniformly mixing comprises the following steps: stirring for 10-30 minutes at room temperature.
Optionally, the drying is freeze drying.
Optionally, the freeze-drying is performed in a freeze-dryer using liquid nitrogen.
Optionally, the conditions of freeze-drying are: the drying temperature is-100 to-25 ℃; the drying air pressure is 10-40 Pa; the drying time is 1-5 days.
Optionally, the inactive gas is selected from at least one of nitrogen, argon, helium, neon, argon, krypton, and xenon.
Optionally, the annealing temperature is 200-500 ℃; the annealing time is 2-10 hours.
Optionally, the upper limit of the annealing temperature is selected from 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃ or 500 ℃.
Optionally, the lower limit of the annealing temperature is selected from 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃ or 450 ℃.
Optionally, the annealing temperature is 300 ℃; the annealing time was 4 hours.
As a specific embodiment, the invention is realized by the following steps: a preparation method of intrinsic defect ruthenium dioxide/graphene two-dimensional material comprises the following steps:
(1) dissolving a ruthenium precursor and graphene oxide by using deionized water to prepare a solution, wherein the ruthenium precursor is ruthenium trichloride or ruthenium trichloride hydrate.
(2) And (2) freezing the mixed solution obtained in the step (1), and then placing the frozen product in a freeze dryer to remove water, so as to obtain the ruthenium precursor/graphene oxide two-dimensional material, wherein the freeze drying is implemented by freezing with liquid nitrogen and drying with the freeze dryer.
(3) Performing air isolation annealing on the ruthenium precursor/graphene oxide two-dimensional material obtained in the step (2), wherein the air isolation annealing is to isolate air from a sample by using one or a combination of argon and nitrogen; the annealing temperature is 200-500 ℃.
According to a third aspect of the present application, there are provided the ruthenium dioxide/graphene two-dimensional material provided according to the first aspect of the present application, and an application of the ruthenium dioxide/graphene two-dimensional material obtained according to the preparation method provided by the second aspect of the present application as an oxygen evolution electrocatalyst.
Currently, all ruthenium dioxide preparation methods anneal a ruthenium precursor in open oxygen sources such as air and oxygen to oxidize the ruthenium precursor into ruthenium dioxide. This results in a large excess of oxygen for the ruthenium precursor. Therefore, the key to the preparation of ruthenium dioxide with intrinsic oxygen defects is the control of the supply of the oxygen source. The method of regulating the supply of the oxygen source is usually to change the concentration of oxygen in the gas, but the catalyst is usually in the form of a powder stack, and the surface of the powder stack is not in contact with the catalyst inside the powder stack to the same extent, which causes the ruthenium precursor on the surface of the powder stack to be oxidized into ruthenium dioxide, while the ruthenium precursor inside the powder stack cannot be prepared into defective ruthenium dioxide due to oxygen-poor decomposition into metallic ruthenium. The surface of the graphene oxide contains rich oxygen functional groups, and the graphene oxide can be theoretically used as an oxygen source to oxidize a ruthenium precursor. In view of this, the strategy of the present application is to oxidize the ruthenium precursor to ruthenium dioxide with oxidized graphene as the substrate for ruthenium dioxide and at the same time as the source of oxygen. On the other hand, the high conductivity of the electrode also plays an important role in improving the oxygen evolution activity of ruthenium dioxide, but the resistance of the commercial ruthenium dioxide electrode is at the level of 2000 Ω, and the conductivity is poor. Graphene (G) has high conductivity, excellent chemical stability and high specific surface area, and is an excellent choice for a catalyst support.
In the present application, "room temperature" means 15 to 35 ℃.
The beneficial effects that this application can produce include:
1) the ruthenium dioxide/graphene two-dimensional material provided by the application has an intrinsic oxygen-deficient ruthenium dioxide structure, does not need to be corroded by an acid solution, and effectively solves the problem that the ruthenium dioxide oxygen-deficient structure can only be generated in the acid solution, which cannot be realized by the existing preparation method.
2) The ruthenium dioxide/graphene two-dimensional material provided by the application has excellent electrocatalytic oxygen evolution activity in acidic and alkaline electrolytes, is convenient to popularize and apply, and provides a basic guarantee for the industrial application of electrocatalytic decomposition water.
3) The ruthenium dioxide/graphene two-dimensional material provided by the application has better conductivity than ruthenium dioxide.
4) According to the defect ruthenium dioxide/graphene two-dimensional material prepared by the preparation method provided by the application, the material prepared by the method has an intrinsic oxygen defect ruthenium dioxide structure by using the graphene oxide ruthenium oxide precursor, the problem that oxygen vacancies are generated only by acid corrosion is effectively solved, the ruthenium dioxide material with ultrahigh electrocatalytic oxygen evolution activity in acidic and alkaline solutions is obtained, and the high-activity and high-adaptability oxygen evolution electrocatalyst is obtained in a real sense.
Drawings
Fig. 1 is a flow chart of the preparation of the ruthenium dioxide/graphene two-dimensional material according to example 1 of the present application.
Fig. 2 is an X-ray diffraction pattern of the ruthenium dioxide/graphene two-dimensional material according to example 1 of the present application.
Fig. 3 is a scanning electron microscope image of the ruthenium dioxide/graphene two-dimensional material according to the embodiment 1 of the present application.
Fig. 4 is a transmission electron microscope image of the ruthenium dioxide/graphene two-dimensional material according to the embodiment 1 of the present application.
Fig. 5 is an atomic force microscope image of the ruthenium dioxide/graphene two-dimensional material according to example 1 of the present application.
Fig. 6 is a drawing of nitrogen gettering for ruthenium dioxide/graphene two-dimensional material according to example 1 of the present application.
FIG. 7 is a graph of the performance of the ruthenium dioxide/graphene two-dimensional material according to the present application in electrocatalytic decomposition of water and oxygen with electrolyte of 0.5M H and conventional ruthenium dioxide2SO4An aqueous solution.
Fig. 8 is a graph of the performance of electrocatalytic decomposition of water and oxygen evolution of the ruthenium dioxide/graphene two-dimensional material according to the embodiment 1 of the present application and the conventional ruthenium dioxide, wherein the electrolyte is 1M KOH aqueous solution.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the starting materials in the examples of the present application were purchased commercially, wherein ruthenium chloride, ruthenium trichloride hydrate were purchased from alladin; the graphene oxide is self-made.
The analysis method in the examples of the present application is as follows:
the X-ray diffraction pattern test method comprises the following steps: powder samples were tested using an X-ray diffractometer (model: Bede D1).
The two-dimensional material scanning electron microscope image testing method comprises the following steps: powder samples were tested using a scanning electron microscope (model JSM-7900F).
The transmission electron microscope image test method comprises the following steps: powder samples were tested using transmission electron microscopy (model JEOL-2100).
The atomic force microscope test method comprises the following steps: the samples were dispersed on a silicon wafer for testing using an atomic force microscope (model number Dimension Icon).
The nitrogen adsorption and desorption test method comprises the following steps: powder sample testing was performed using a gas adsorption apparatus (model number Autosorb iQ).
The Fourier expansion X-ray absorption fine structure spectrum testing method comprises the following steps: powder sample testing was performed using a Shanghai light source.
The test method of the electrocatalytic oxygen evolution performance comprises the following steps: the powder sample test was carried out using an electrochemical workstation (model: CHI 760).
Example 1 preparation method of defective ruthenium dioxide/graphene two-dimensional material
Fig. 1 shows a preparation flow chart of a ruthenium dioxide/graphene two-dimensional material, and the ruthenium dioxide/graphene two-dimensional material is prepared according to the process flow shown in fig. 1, and the specific operation steps are as follows:
(1) and preparing a graphene oxide solution with the content of 1mg/mL by using deionized water, wherein the volume of the graphene oxide solution is 20 mL.
(2) Deionized water is used for preparing 0.5mL of ruthenium trichloride hydrate solution with the content of 20 mg/mL.
(3) And (3) dripping the ruthenium trichloride hydrate solution into the graphene oxide solution for 10 minutes, and stirring at room temperature for 20 minutes to enable ruthenium trichloride to be adsorbed to the surface of the graphene oxide.
(4) And (4) freezing the mixed solution obtained in the step (3) into ice blocks by using liquid nitrogen, and putting the obtained ice blocks into a freeze dryer to remove moisture in the solid to obtain the solid ruthenium trichloride hydrate/graphene oxide two-dimensional material. The temperature in the freeze-drying machine is-50 deg.C, the air pressure is 23Pa, and the freeze-drying time is 2 days.
(5) And (4) putting the ruthenium trichloride hydrate/graphene oxide two-dimensional material obtained in the step (4) into a tube furnace, and annealing at 300 ℃ for 4 hours under the protection of argon gas to obtain the defect ruthenium dioxide/graphene two-dimensional material. The mass ratio of the graphene to the ruthenium dioxide in the ruthenium dioxide/graphene two-dimensional material is 1: 2.
example 2 preparation method of defective ruthenium dioxide/graphene two-dimensional material
(1) And preparing 20mL of graphene oxide solution with the content of 0.5mg/mL by using deionized water.
(2) Deionized water is used for preparing 0.5mL of ruthenium trichloride hydrate solution with the content of 10 mg/mL.
(3) And (3) dripping the ruthenium trichloride hydrate solution into the graphene oxide solution for 20 minutes, and stirring at room temperature for 10 minutes to enable ruthenium trichloride to be adsorbed to the surface of the graphene oxide.
(4) And (4) freezing the mixed solution obtained in the step (3) into ice blocks by using liquid nitrogen, and putting the obtained ice blocks into a freeze dryer to remove moisture in the solid to obtain the solid ruthenium trichloride hydrate/graphene oxide two-dimensional material. The temperature in the freeze-drying machine is-25 deg.C, the air pressure is 40Pa, and the freeze-drying time is 5 days.
(5) And (4) putting the ruthenium trichloride hydrate/graphene oxide two-dimensional material obtained in the step (4) into a tube furnace, and annealing at 500 ℃ for 2 hours under the protection of argon gas to obtain a defect ruthenium dioxide/graphene two-dimensional material. The mass ratio of the graphene to the ruthenium dioxide in the ruthenium dioxide/graphene two-dimensional material is 1: 5.
example 3 preparation method of defective ruthenium dioxide/graphene two-dimensional material
(1) And preparing 20mL of graphene oxide solution with the content of 5mg/mL by using deionized water.
(2) 0.5mL of ruthenium trichloride hydrate solution with the content of 100mg/mL is prepared by deionized water.
(3) And (3) dripping the ruthenium trichloride hydrate solution into the graphene oxide solution for 5 minutes, and stirring at room temperature for 30 minutes to enable ruthenium trichloride to be adsorbed to the surface of the graphene oxide.
(4) And (4) freezing the mixed solution obtained in the step (3) into ice blocks by using liquid nitrogen, and putting the obtained ice blocks into a freeze dryer to remove moisture in the solid to obtain the solid ruthenium trichloride hydrate/graphene oxide two-dimensional material. The temperature in the freeze-drying machine is-100 deg.C, the air pressure is 10Pa, and the freeze-drying time is 1 day.
(5) And (4) putting the ruthenium trichloride hydrate/graphene oxide two-dimensional material obtained in the step (4) into a tube furnace, and annealing at 200 ℃ for 10 hours under the protection of nitrogen to obtain the defect ruthenium dioxide/graphene two-dimensional material. The mass ratio of the graphene to the ruthenium dioxide in the ruthenium dioxide/graphene two-dimensional material is 1: 2.
and (3) product analysis:
the ruthenium dioxide/graphene two-dimensional material prepared in example was analyzed, and the ruthenium dioxide/graphene two-dimensional material prepared in example 1 was used as a representative, and the product was analyzed.
The defective ruthenium dioxide/graphene two-dimensional material prepared in example 1 was analyzed by an X-ray diffractometer, and the X-ray diffraction pattern obtained is shown in fig. 2. Figure 2 shows a typical rutile ruthenium dioxide phase, demonstrating the ruthenium in the defective ruthenium dioxide/graphene two-dimensional material is a ruthenium dioxide structure.
Scanning electron microscope characterization is performed on the defective ruthenium dioxide/graphene two-dimensional material in the embodiment 1, and the result is shown in fig. 3, as can be seen from fig. 3, the defective ruthenium dioxide/graphene two-dimensional material is in a sheet shape, the thickness of the sheet is within the range of 1-10 nm, and the result shows that: the defect ruthenium dioxide/graphene two-dimensional material is an ultrathin nanosheet.
The defect ruthenium dioxide/graphene two-dimensional material in example 1 is characterized by a transmission electron microscope, and the result is shown in fig. 4, and in fig. 4, ruthenium dioxide particles composed of (110) crystal planes and near-transparent graphene can be seen, which indicates that: the defect ruthenium dioxide/graphene two-dimensional material is composed of ruthenium dioxide and graphene.
The atomic force microscope characterization is performed on the defective ruthenium dioxide/graphene two-dimensional material in the embodiment 1, and the result is shown in fig. 5, as can be seen from fig. 5, the ruthenium dioxide/graphene two-dimensional material is in a sheet structure, and the thickness of the defective ruthenium dioxide/graphene two-dimensional material is 9 nanometers.
The defect ruthenium dioxide/graphene two-dimensional material in example 1 was subjected to nitrogen adsorption and desorption characterization, and the result is shown in fig. 6, in which the curve formed by connecting solid dots represents an adsorption curve, and the curve formed by connecting black squares represents a desorption curve. The results show that: the specific surface area of the defective ruthenium dioxide/graphene two-dimensional material is 125m2g-1。
And (3) performance testing:
the ruthenium dioxide/graphene two-dimensional material prepared in the example was subjected to a performance test, and the ruthenium dioxide/graphene two-dimensional material prepared in example 1 was used as a representative, and the product was subjected to a performance test.
The defect ruthenium dioxide/graphene two-dimensional material prepared in the example 1 is subjected to electrocatalytic decomposition water oxygen evolution performance characterization, and the results are shown in fig. 7 and 8, wherein in fig. 7, a curve 1 represents a polarization curve of the ruthenium dioxide/graphene two-dimensional material in an acid solution, a curve 2 represents a polarization curve of commercial ruthenium dioxide in the acid solution, and the current density of the curve 1 is far higher than that of the curve 2 under the same voltage; in fig. 8, curve 3 represents the polarization curve of the ruthenium dioxide/graphene two-dimensional material in the alkaline solution, curve 4 represents the polarization curve of the commercial ruthenium dioxide in the alkaline solution, and the current density of curve 3 is much higher than that of curve 4 under the same voltage; the performance of the defect ruthenium dioxide/graphene two-dimensional material in acidic and alkaline electrolytes is obviously superior to that of ruthenium dioxide sold on the market, and the efficient electrocatalytic oxygen evolution in various electrolytes is realized.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A ruthenium dioxide/graphene two-dimensional material, comprising:
graphene;
ruthenium dioxide adsorbed on the graphene;
wherein the ruthenium dioxide/graphene two-dimensional material has intrinsic defects.
2. The two-dimensional material according to claim 1, wherein the thickness of the ruthenium dioxide/graphene two-dimensional material is 1-20 nm;
preferably, the specific surface area of the ruthenium dioxide/graphene two-dimensional material is 50-300 m2g-1；
Preferably, the coordination number of Ru in the ruthenium dioxide/graphene two-dimensional material is less than 6;
preferably, the mass ratio of the graphene to the ruthenium dioxide in the ruthenium dioxide/graphene two-dimensional material is 5-95: 100.
3. The method for preparing a ruthenium dioxide/graphene two-dimensional material according to claim 1 or 2, comprising:
a) preparing a solution containing a ruthenium precursor and graphene oxide;
b) drying the solution; and
c) annealing the solid dried in the step b) in the presence of inactive gas to obtain the ruthenium dioxide/graphene two-dimensional material.
4. A production method according to claim 3, wherein the ruthenium precursor is selected from ruthenium trichloride or ruthenium trichloride hydrate.
5. The method for preparing according to claim 3, wherein the step a) comprises:
respectively preparing a graphene oxide dispersion liquid and a solution containing a ruthenium precursor;
adding the solution containing the ruthenium precursor into the graphene oxide dispersion liquid and uniformly mixing;
preferably, the solvent of the graphene oxide dispersion liquid is water, and the concentration of the solvent is 0.5-5 g/L;
the solvent of the ruthenium precursor-containing solution is water, and the concentration of the water is 10-100 g/L.
6. The production method according to claim 5, wherein the concentration of the graphene oxide dispersion liquid is 1 g/L;
the concentration of the solution containing the ruthenium precursor is 20 g/L;
preferably, the adding is dropwise adding, and the dropwise adding time is 5-20 minutes;
the uniformly mixing comprises the following steps: stirring for 10-30 minutes at room temperature.
7. The method according to claim 3, wherein the drying is freeze-drying;
preferably, the freeze-drying is carried out in a freeze-dryer using liquid nitrogen;
preferably, the conditions of freeze-drying are:
the drying temperature is-100 to-25 ℃;
the drying air pressure is 10-40 Pa;
the drying time is 1-5 days.
8. The method of claim 3, wherein the inert gas is at least one selected from the group consisting of nitrogen, argon, helium, neon, argon, krypton, and xenon.
9. The method according to claim 3, wherein the annealing temperature is 200 to 500 ℃;
the annealing time is 2-10 hours;
preferably, the annealing temperature is 300 ℃;
the annealing time was 4 hours.
10. The ruthenium dioxide/graphene two-dimensional material as defined in any one of claims 1 to 2 and the ruthenium dioxide/graphene two-dimensional material prepared by the preparation method as defined in any one of claims 3 to 9 are used as an oxygen evolution electrocatalyst.
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