CN113293402A - Ruthenium monoatomic/graphite alkyne film and preparation method and application thereof - Google Patents
Ruthenium monoatomic/graphite alkyne film and preparation method and application thereof Download PDFInfo
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- CN113293402A CN113293402A CN202110514757.2A CN202110514757A CN113293402A CN 113293402 A CN113293402 A CN 113293402A CN 202110514757 A CN202110514757 A CN 202110514757A CN 113293402 A CN113293402 A CN 113293402A
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a ruthenium monoatomic/graphite alkyne membrane as well as a preparation method and application thereof, and solves the problems that the existing catalyst for hydrogen production by water electrolysis is high in price and easy to generate catalyst poisoning phenomenon. The ruthenium monoatomic/graphite alkyne film provided by the invention is composed of ruthenium monoatomic and graphite alkyne films which are combined through chemical stabilization. The preparation method comprises the following steps: and (2) taking the graphite alkyne film as a carrier, soaking the prepared graphite alkyne in aqueous solution of a ruthenium compound and sulfuric acid, and carrying out reduction reaction through electro-reduction to obtain the ruthenium monoatomic/graphite alkyne structure. The method has the advantages of simple process, environmental protection, and good reaction stability of the ruthenium monoatomic/graphite alkyne material, and the ruthenium monoatomic/graphite alkyne film has good hydrogen production performance by water electrolysis due to the highly exposed and dispersed catalytic active sites, and can be expected to be used as a novel efficient hydrogen production catalyst material by water electrolysis.
Description
Technical Field
The invention relates to the field of chemistry and materials, in particular to a ruthenium monoatomic/graphite alkyne film and a preparation method and application thereof.
Background
The water electrolysis hydrogen production technology is an effective way for obtaining green energy hydrogen energy in the future. Platinum is used as an efficient water electrolysis hydrogen production catalyst, is high in price, low in earth reserve, easy to generate a catalyst poisoning phenomenon, and not beneficial to the harmonious development of hydrogen energy and hydrogen economy, so that the exploration of an efficient non-noble metal electrocatalyst has profound significance for the regeneration and efficient reasonable utilization of hydrogen energy.
The carbon material has excellent physical and chemical properties, and the modification of metal single atoms on the surface of the carbon material has important application in nano science and technology. The successful preparation of graphdiyne (y.l.li, et al chem.commun., 2010, 46, 3256-. The graphdiyne has a special electronic structure, a large specific surface and a porous structure, and excellent chemical, optical and thermal stability and electrical properties. The use of metal monoatomic atoms in catalysis, in particular in the electrolysis of water, has received considerable attention (S. Guo, adv. Energy Mater. 2020, 10, 1903120. Y. Li, chem. Soc. Rev., 2020,49, 2215-. Due to the low-dimensional structure of the two-dimensional carbon-based material loaded monatomic catalyst, the highly exposed active sites show superior performance in the application of the catalyst for hydrogen production by water electrolysis, and the catalyst is expected to become a novel efficient catalyst material for hydrogen production by water electrolysis.
Disclosure of Invention
The invention provides a ruthenium monoatomic/graphite alkyne film (Ru-SACs/GDY for short) and a preparation method and application thereof, which solve the problems that the existing catalyst for hydrogen production by water electrolysis is high in price and easy to generate catalyst poisoning phenomenon.
The technical scheme adopted by the invention is as follows:
a ruthenium monoatomic/graphite alkyne film is composed of a ruthenium monoatomic and a graphite alkyne film which are combined through chemical stabilization, and the ruthenium monoatomic is distributed on the surface of the graphite alkyne film.
The particle size of the ruthenium monoatomic film is 0.25-0.5 nm, and the mass ratio of the ruthenium monoatomic film to the graphite alkyne film is 1: 100.
The lattice fringe spacing of the ruthenium monoatomic/graphite alkyne film is 0.32 nm; the lattice fringe spacing of the graphyne film is 0.365 nm.
A preparation method of a ruthenium monoatomic/graphite alkyne film comprises the following steps: dipping the graphite alkyne film in ruthenium-containing solution with the concentration of 1-5 mol/L by taking the graphite alkyne film as a carrierIn an aqueous solution of a compound and sulfuric acid with a concentration of 0.2-0.8 mol/L, the mass ratio of the ruthenium-containing compound to the sulfuric acid is 1: 125-4:125, and carrying out reduction reaction through electric reduction, wherein the current density in the electric reduction reaction is 1-10 mA/cm2And the current duration is 40-200s, and the ruthenium monoatomic/graphite alkyne film is obtained after the reaction is finished.
The current density is 10 mA/cm2The current duration was 40 s.
The mass ratio of the ruthenium-containing compound to the sulfuric acid is 1: 125.
the concentration of the aqueous solution of the ruthenium-containing compound is 2mol/L, and the concentration of sulfuric acid is 0.5 mol/L.
The ruthenium-containing compound is at least one selected from ruthenium chloride and chlororuthenic acid.
The invention also belongs to the protection scope of the invention, the ruthenium monoatomic/graphite alkyne film is put into deionized water, the electrolytic voltage is 220V, and the hydrogen evolution reaction is carried out at the current density of 10 mA/cm2Has an overpotential of 44mV and an oxygen evolution reaction at a current density of 10 mA/cm2The overpotential of (2) is 531 mV.
The invention has the beneficial effects that:
the preparation method of the ruthenium monoatomic/graphite alkyne film is simple and convenient, green and environment-friendly, has good reaction stability and highly exposed and dispersed catalytic active sites, and has better hydrogen production performance by water electrolysis; and is also expected to be a novel efficient catalyst material for hydrogen production by water electrolysis.
Drawings
FIG. 1 is a scanning electron micrograph and a transmission electron micrograph of Ru-SACs/GDY prepared according to the example.
FIG. 2 is an X-ray powder diffraction (XRD) pattern of Ru-SACs/GDY and GDY prepared in accordance with the examples.
FIG. 3 is an X-ray photoelectron Spectroscopy (XPS) of example prepared Ru-SACs/GDY.
FIG. 4 is an X fine ray electron spectrum (EXAFS) of example prepared Ru-SACs/GDY.
FIG. 5 is a polarization curve and a Tafel curve of hydrogen evolution reaction under the action of Ru-SACs/GDY catalyst in an electrolytic cell.
FIG. 6 shows the mass activity, switching frequency and reaction stability of the oxygen evolution reaction under the action of the Ru-SACs/GDY catalyst in the cell.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The graphone films described in the following examples were prepared according to the methods provided in the following references: guying Li, Yuliang Li, Huibiao Liu, Yanbing Guo, Yongjun Li, Daoben Zhu, architecture of Graphdiyne Nanoscale films, chem, Comm.2010, 46, 3256-. The preparation method comprises the following steps: a three-necked flask was charged with 1.1040 g (g) (2.00 mmol) hexabromobenzene, 500 mg (mg) (0.400mmol) Pd (PPh3)4, 25mL (mL) toluene and a solution of trimethylsilylethynyl zinc chloride (20.0mmol) in 40 mL (mL) tetrahydrofuran. The reaction mixture was stirred at 80 ℃ for 3 days under nitrogen atmosphere, after completion of the reaction, 20mL of dilute hydrochloric acid (1 mol/l) was added to the reaction mixture, extracted with ethyl acetate, and the organic layers were combined, washed with brine and twice with water, then dried over anhydrous magnesium sulfate, concentrated to dryness, and purified by column chromatography (eluent: n-hexane/dichloromethane: 17/3) to obtain 910mg of compound 1 (yield: 69.6%). To a solution of 43.6 mg (mg) (0.066 mmol) of compound 1 in Tetrahydrofuran (THF) at 8 ℃ was added 0.4mL tetrabutylammonium fluoride (TBAF) (1 mol/l (M) solution in tetrahydrofuran, 0.4mmol) and the reaction was stirred under nitrogen for 10 min; then the reaction solution was diluted with ethyl acetate (20 mL), washed three times with saturated saline, dried over anhydrous sodium sulfate (10 g), and concentrated to dryness to give hexaynylbenzene (compound 2) (9.08mg, 62%), and compound 2 was dissolved with 25mL of pyridine, and slowly dropped into a three-necked flask containing 50mL of pyridine and copper sheet (4 cm) under nitrogen protection (the temperature of the reaction solution was 60 ℃), and the dropping time was 24 hours; and then continuously stirring and reacting for 3 days at 60 ℃, generating a layer of black film on the copper sheet after the reaction is finished, and washing the copper sheet by using acetone and N, N-Dimethylformamide (DMF) in sequence, wherein the black film is the graphite alkyne film (2.7mg, 24.3%).
When the obtained Ru-SACs/GDY is subjected to TEM detection, a sample is prepared according to the following method: dissolving the copper sheet loaded with the ruthenium monoatomic/graphite alkyne in a nitric acid solution, washing with water, acetone and ethanol in sequence, centrifuging, finally dispersing with ethanol, taking 10 microliters of uniformly dispersed suspension, and slowly dripping the suspension on a copper net.
Example (b):
to 1 liter (L) of water were added successively 2 mmol of the compound chlororuthenic acid (2 mmol, 0.415 g, 2 mmol/L) and 0.5mol of sulfuric acid (0.5mol/L), and the prepared graphdiyne was immersed therein and stirred at room temperature for 2 hours (h). Then the solution is pumped in current with the density of 10 mA/cm2Constant current for 40 seconds. And washing with secondary water to obtain the ruthenium monoatomic/graphite alkyne film provided by the invention.
The ruthenium monoatomic/graphite alkyne film consists of ruthenium monoatomic atoms and a graphite alkyne film which are combined through chemical stabilization, and the ruthenium monoatomic atoms are monodisperse on the surface of the graphite alkyne film.
FIG. 1 is a Scanning Electron Micrograph (SEM) and a Transmission Electron Micrograph (TEM) of Ru-SACs/GDY, from which it can be seen that the Ru single atoms are uniformly distributed on the graphdine film and have a uniform particle size of 0.38 nm. + -. 0.01nm, and the high resolution TEM shows a GDY lattice structure with a plane spacing of 0.321 nm corresponding to the GDY (001) plane.
FIG. 2 is an X-ray powder diffraction (XRD) spectrum of Ru-SACs/GDY, wherein the diffraction peak at 26 corresponds to the diffraction peak of graphdiyne, and no diffraction peak of ruthenium particles is observed.
Meanwhile, an X-ray photoelectron spectrometer is also utilized to analyze the element composition of the Ru-SACs/GDY, and FIG. 3 shows that the Ru-SACs/GDY consists of carbon elements and ruthenium elements, wherein FIG. 3b is a Ru 3p peak of the ruthenium elements, which shows that a ruthenium single atom is successfully modified on the graphite alkyne film, 284.8eV is a C1 s peak of the carbon elements in the graphite alkyne film, and the oxygen element peak at 532eV is caused by air adsorption of the graphite alkyne.
FIG. 4 is a broad X-ray absorption fine structure map of Ru-SACs/GDY showing that there is a major peak at 1.54A corresponding to Ru-C action, illustrating the presence of a single atom of ruthenium; meanwhile, the valence of Ru atom is +4 from the K edge spectrum of Ru, which shows that Ru is anchored at GDY with the highest valence.
FIG. 5 is a graph comparing the hydrogen evolution performance of several catalysts, and it can be seen that Ru-SACs/GDY possesses the best hydrogen evolution activity (at a current density of 10 mA/cm)2Over-potential of 44 mV).
FIG. 6 shows the mass activity, switching frequency and reaction stability of oxygen evolution reaction by Ru-SACs/GDY catalyst in the electrolytic cell, the mass activity of Ru-SACs/GDY catalyst was up to 9.03A/mgmetal at an overpotential of 2.0V, and at the same time, showed the highest switching frequency (TOF) of 7.09/s, and the polarization curve remained consistent with the initial curve after 2000 cycles of voltammograms in an acidic environment.
The foregoing description of the embodiments is merely a preferred embodiment of the invention to facilitate those of ordinary skill in the art in understanding and using the invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. It should be noted that the present invention is not limited to the above-mentioned embodiments, and those skilled in the art should be able to make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (9)
1. A ruthenium monoatomic/graphite alkyne film is characterized in that: the chemical stabilizing film consists of ruthenium monoatomic atoms and a graphite alkyne film which are combined through chemical stabilizing action, wherein the ruthenium monoatomic atoms are distributed on the surface of the graphite alkyne film.
2. The ruthenium monatomic/graphdiyne membrane of claim 1, wherein: the particle size of the ruthenium monoatomic film is 0.25-0.5 nm, and the mass ratio of the ruthenium monoatomic film to the graphite alkyne film is 1: 100.
3. A preparation method of a ruthenium monoatomic/graphite alkyne film comprises the following steps: dipping a graphite alkyne film in an aqueous solution of a ruthenium-containing compound with the concentration of 1-5 mol/L and sulfuric acid with the concentration of 0.2-0.8 mol/L by taking the graphite alkyne film as a carrier, wherein the mass ratio of the ruthenium-containing compound to the sulfuric acid is 1: 125-4:125, and carrying out reduction reaction through electric reduction, wherein the current density in the electric reduction reaction is 1-10 mA/cm2And the current duration is 40-200s, and the ruthenium monoatomic/graphite alkyne film is obtained after the reaction is finished.
4. The method for preparing a ruthenium monatomic/graphdiyne membrane according to claim 3, wherein: the current density is 10 mA/cm2The current duration was 40 s.
5. The method for preparing a ruthenium monatomic/graphdiyne membrane according to claim 3, wherein: the mass ratio of the ruthenium-containing compound to the sulfuric acid is 1: 125.
6. the method for preparing a ruthenium monatomic/graphdiyne membrane according to claim 3, wherein: the concentration of the aqueous solution of the ruthenium-containing compound is 2mol/L, and the concentration of sulfuric acid is 0.5 mol/L.
7. The method for preparing a ruthenium monatomic/graphdiyne membrane according to claim 3, wherein: the ruthenium-containing compound is at least one selected from ruthenium chloride and chlororuthenic acid.
8. Use of the ruthenium monatomic/graphyne film according to claims 1 to 2 for the electrolysis of water.
9. The use of claim 8, wherein: putting the ruthenium monoatomic/graphite alkyne film into deionized water, electrolyzing at 220V, and reacting for hydrogen evolution at current density of 10 mA/cm2Has an overpotential of 44mV and an oxygen evolution reaction at a current density of 10 mA/cm2The overpotential of (2) is 531 mV.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102350345A (en) * | 2011-07-07 | 2012-02-15 | 中国科学院化学研究所 | Gold nanoparticle / graphite alkyne composite membrane, preparation method and application thereof |
| CN111384409A (en) * | 2020-02-25 | 2020-07-07 | 南京师范大学 | Nitrogen-doped graphite alkyne-riveted transition metal monoatomic catalyst and preparation method and application thereof |
| CN111389394A (en) * | 2020-03-04 | 2020-07-10 | 南方科技大学 | Metal monatomic catalyst and preparation method thereof |
| CN111490258A (en) * | 2020-05-12 | 2020-08-04 | 超威电源集团有限公司 | Preparation method of graphite alkyne-loaded monatomic catalyst |
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- 2021-05-12 CN CN202110514757.2A patent/CN113293402A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102350345A (en) * | 2011-07-07 | 2012-02-15 | 中国科学院化学研究所 | Gold nanoparticle / graphite alkyne composite membrane, preparation method and application thereof |
| CN111384409A (en) * | 2020-02-25 | 2020-07-07 | 南京师范大学 | Nitrogen-doped graphite alkyne-riveted transition metal monoatomic catalyst and preparation method and application thereof |
| CN111389394A (en) * | 2020-03-04 | 2020-07-10 | 南方科技大学 | Metal monatomic catalyst and preparation method thereof |
| CN111490258A (en) * | 2020-05-12 | 2020-08-04 | 超威电源集团有限公司 | Preparation method of graphite alkyne-loaded monatomic catalyst |
Non-Patent Citations (1)
| Title |
|---|
| HUIDI YU等: "2D graphdiyne loading ruthenium atoms for high efficiency water splitting", 《NANO ENERGY》, vol. 72, pages 104667 * |
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Inventor after: Huang Lina Inventor after: Ju Bingxin Inventor before: Shen Zhemin |
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