CN112899724B - Nano ruthenium dioxide coated ruthenium loaded carbon micron sheet, and preparation method and application thereof - Google Patents

Nano ruthenium dioxide coated ruthenium loaded carbon micron sheet, and preparation method and application thereof Download PDF

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CN112899724B
CN112899724B CN202011439061.XA CN202011439061A CN112899724B CN 112899724 B CN112899724 B CN 112899724B CN 202011439061 A CN202011439061 A CN 202011439061A CN 112899724 B CN112899724 B CN 112899724B
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ruthenium dioxide
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章根强
李亚鹏
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University of Science and Technology of China USTC
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Abstract

The invention provides a preparation method of a nanoscale ruthenium dioxide coated ruthenium loaded carbon micron sheet, compared with the prior art, the nanoscale ruthenium dioxide coated ruthenium loaded carbon micron sheet prepared by the invention has the characteristics of high loading capacity and high dispersion, and has large specific surface area and a large amount of mesoporous structures, the conductivity of the material is improved by chemically coupling tiny ruthenium dioxide coated ruthenium nanoparticles and carbon, the electronic structure of the material is improved by improving the loading capacity of the ruthenium dioxide coated ruthenium nanoparticles, the number of active sites is increased, meanwhile, the existence of a large specific surface area and a large amount of mesoporous structures is beneficial to electrolyte permeation and gas release, and the electrocatalytic activity and stability of the material are synergistically improved; the preparation method is simple, consists of simple adsorption, calcination and oxidation, has strong operability, is easy to repeat, has good stability, is easy for large-scale production, and can meet the actual requirements of full-hydrolysis hydrogen production.

Description

Nano-scale ruthenium dioxide coated ruthenium-loaded carbon micron sheet, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a nanoscale ruthenium dioxide coated ruthenium loaded carbon micron sheet, and a preparation method and application thereof.
Background
Hydrogen is a clean and efficient secondary energy carrier, and provides an ideal alternative energy way for fundamentally solving global problems of energy, environment and the like for human beings. The hydrogen production by electrolyzing water is an ideal method for preparing high-purity hydrogen and is an important component of modern clean energy technology.
The electrolysis of water is formed by two half reactions of cathodic Hydrogen Evolution (HER) and anodic Oxygen Evolution (OER), the overpotential of the electrolyzed water for hydrogen production can be reduced by using an electrochemical catalyst, so that the energy conversion efficiency is improved, however, due to the slow four-electron reaction of the anode, the overpotential of 600-800 mV is usually required to be overcome for commercial electrolyzed water for effective hydrogen production, the stability is poor, meanwhile, the currently reported better hydrogen production and oxygen production catalysts are respectively realized under acidic and alkaline conditions, the complexity and the cost of an electrolyzed water device are increased, and therefore, the development of an effective electrolyzed water catalyst, particularly a bifunctional catalyst with universal pH, is crucial to the realization of the efficient utilization of the electrolyzed water for hydrogen production.
Ruthenium-based materials are accepted as OER-based catalysts, but their performance is still far from the currently reported nickel iron oxide/oxyhydroxide isoelectric catalysts, possibly due to their fewer active sites and poorer conductivity. Meanwhile, at present, the ruthenium-based nano material has reported HER activity similar to platinum in acidity and alkalinity, mainly due to smaller size and inherent high catalytic activity, which indicates that the ruthenium-based nano material has potential excellent difunctional full-hydrolytic activity, but the report on the full-hydrolytic activity is few, and the catalytic performance of the ruthenium-based nano material still needs to be improved.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a nanoscale ruthenium dioxide coated ruthenium-loaded carbon micron sheet, a preparation method and an application thereof, wherein the nanoscale ruthenium dioxide coated ruthenium-loaded carbon micron sheet prepared by the method has high loading capacity and good dispersibility, can greatly reduce overpotential of full-hydrolysis in different environments such as acidic environment and alkaline environment, has good stability, and provides a new idea for designing an excellent bifunctional full-hydrolysis hydrocatalyst with general pH.
The invention provides a preparation method of a nanometer ruthenium dioxide coated ruthenium loaded carbon micron sheet, which comprises the following steps:
s1) dispersing ruthenium salt and an organic carbon source in an alcohol solvent, mixing, and performing solid-liquid separation to obtain a precursor; the organic carbon source contains nitrogen;
or mixing and grinding ruthenium salt and an organic carbon source to obtain a precursor;
s2) carrying out high-temperature calcination on the precursor in a reducing atmosphere to obtain an intermediate product;
s3) calcining the intermediate product at low temperature in air atmosphere to obtain the nano ruthenium dioxide coated ruthenium loaded carbon micron sheet.
Preferably, the ruthenium salt is selected from ruthenium trichloride; the organic carbon source is selected from one or more of melamine, dicyandiamide and hexamethylenetetramine.
Preferably, the molar ratio of the ruthenium salt to the organic carbon source is 1: (10-60).
Preferably, the mixing time in the step S1) is 10-60 min; the solid-liquid separation is carried out by adopting a centrifugal method; the centrifugation speed is 5000-10000 rpm; the centrifugation time is 1-5 min;
the mixing and grinding time is 10-60 min.
Preferably, the temperature rise rate of the high-temperature calcination in the step S2) is 2-10 ℃/min; the high-temperature calcination temperature is 600-900 ℃; the high-temperature calcination time is 1-3 h.
Preferably, the heating rate of the low-temperature calcination in the step S3) is 2-5 ℃/min; the low-temperature calcination temperature is 200-320 ℃; and the low-temperature calcination time is 1-4 h.
Preferably, the volume content of hydrogen in the reducing atmosphere is 5-15%.
The invention also provides the nanometer ruthenium dioxide coated ruthenium loaded carbon micron sheet prepared by the method, which is characterized in that the nanometer ruthenium dioxide coated ruthenium loaded carbon micron sheet is in a porous micron sheet structure consisting of nanometer ruthenium dioxide coated ruthenium, and carbon elements and nitrogen elements are distributed on the micron sheet.
Preferably, the loading amount of the ruthenium dioxide in the nanoscale ruthenium dioxide coated ruthenium-loaded carbon micron sheet is 85-95 wt%; the nano ruthenium dioxide coated ruthenium loaded carbon micron sheet is a porous micron sheet, and the aperture is 1-5 nm; the specific surface area of the nanoscale ruthenium dioxide coated ruthenium-loaded carbon micron sheet is 180-200 m2/g。
The invention also provides application of the nano ruthenium dioxide coated ruthenium loaded carbon micron sheet prepared by the method as a bifunctional full-electrolysis hydroelectric catalyst.
The invention provides a preparation method of a nanoscale ruthenium dioxide coated ruthenium loaded carbon micron sheet, which comprises the following steps: s1) dispersing ruthenium salt and an organic carbon source in an alcohol solvent, mixing, and then carrying out solid-liquid separation to obtain a precursor, or directly mixing solids; the organic carbon source contains nitrogen; s2) calcining the precursor at high temperature in a reducing atmosphere to obtain an intermediate product; s3) calcining the intermediate product at low temperature in air atmosphere to obtain the nano ruthenium dioxide coated ruthenium loaded carbon micron sheet. Compared with the prior art, the nano ruthenium dioxide coated ruthenium loaded carbon micron sheet prepared by the invention has the characteristics of high loading capacity and high dispersion, and has large specific surface area and a large amount of mesoporous structures, the conductivity of the material is improved by chemically coupling the tiny ruthenium dioxide coated ruthenium nanoparticles and carbon, the electronic structure of the material is improved by improving the loading capacity of the ruthenium dioxide coated ruthenium nanoparticles, the number of active sites is increased, and meanwhile, the existence of a large specific surface area and a large amount of mesoporous structures is beneficial to electrolyte permeation and gas release, and the electrocatalytic activity and stability of the material are synergistically improved; the preparation method is simple, consists of simple adsorption, calcination and oxidation, has strong operability, is easy to repeat, has good stability, is easy for large-scale production, and can meet the actual requirements of full-hydrolysis hydrogen production.
Experiments show that the carbon micron sheet loaded with ruthenium coated by the high-loading and high-dispersion nano ruthenium dioxide is 0.5M H2SO4The medium current density is 10mA cm-2The overpotentials of hydrogen production, oxygen production and water decomposition are respectively 46mV, 177mV and 237mV, and the current density is 10mA cm in 1.0M KOH-2The corresponding hydrogen production, oxygen production and water splitting overpotential are respectively 7mV, 201mV and 207mV at 0.05M H2SO4The medium current density is 10mA cm-2The corresponding overpotential of oxygen generation and total hydrolysis is 192mV and 239mV respectively, the hydrogen generation activity is better than or similar to the current commercial Pt/C, the oxygen generation performance is better than the commercial Ru/C or Ir/C catalyst, and the total hydrolysis catalytic performance in acid and alkali is obviously better than Pt/C + RuO2The composite electrode material has good stability.
Drawings
Fig. 1(a) is an XRD spectrum of the nano-scale ruthenium dioxide coated ruthenium supported carbon micron sheet obtained in example 1 of the present invention; (b) is a Raman spectrogram of the nano ruthenium dioxide coated ruthenium loaded carbon micron sheet prepared in the embodiment 1 of the invention; (c) the thermogravimetric graph of the nano-scale ruthenium dioxide coated ruthenium carbon-loaded micron sheet prepared in the embodiment 1 of the invention is shown in the figure; (d) is an isothermal adsorption and desorption curve chart of the nano ruthenium dioxide coated ruthenium carbon-loaded micron sheet prepared in the embodiment 1 of the invention;
FIG. 2(a) is a scanning electron microscope image of the nano-sized ruthenium dioxide coated ruthenium carbon-loaded nanosheet prepared in example 1 of the present invention; (b) and (c) is a transmission electron microscope image of the nano ruthenium dioxide coated ruthenium loaded carbon micron sheet prepared in the embodiment 1 of the invention; (d) a scanning electron microscope image of the spherical aberration correction of the nano ruthenium dioxide coated ruthenium loaded carbon micron sheet prepared in the embodiment 1 of the invention; (e) a high-angle annular dark field diagram and a related element energy spectrogram of the nano ruthenium dioxide coated ruthenium-loaded carbon micron sheet prepared in the embodiment 1 of the invention;
FIG. 3 is a graph showing the distribution of the particle size of the nano-sized ruthenium dioxide coated ruthenium supported carbon micron sheet prepared in example 1 of the present invention;
FIG. 4 is a graph showing the hydrogen production performance of the nano-sized ruthenium dioxide coated ruthenium supported carbon micro-tablets prepared in example 1 of the present invention;
FIG. 5 is a graph of the oxygen evolution performance of the nanoscale ruthenium dioxide coated ruthenium on carbon micron sheet prepared in example 1 of the present invention;
FIG. 6 is a graph showing the full hydrolysis performance of the nano-sized ruthenium dioxide coated ruthenium loaded carbon micron sheet prepared in example 1 of the present invention;
FIG. 7 is a photograph of the nano-sized ruthenium dioxide coated ruthenium supported carbon micron sheet prepared in example 1 of the present invention, which is completely hydrolyzed by 1.5V battery driving;
fig. 8 (a) is a schematic low power transmission electron microscope image of the nanoscale ruthenium dioxide coated ruthenium-supported carbon nanosheet prepared in example 2 of the present invention; (b) is a high-power transmission electron microscope image of the nano ruthenium dioxide coated ruthenium carbon-loaded micron sheet prepared in the embodiment 2 of the invention;
FIG. 9 is an XRD pattern of the nano-sized ruthenium dioxide coated ruthenium supported carbon nanoplatelets prepared according to example 2 of the present invention;
FIG. 10 (a) is a low power transmission electron microscope image of the nano-sized ruthenium dioxide coated ruthenium supported carbon micro-sheet prepared in example 3 of the present invention; (b) is a high-power transmission electron microscope image of the nano ruthenium dioxide coated ruthenium carbon-loaded micron sheet prepared in the embodiment 3 of the invention;
FIG. 11 is an XRD pattern of the nano-sized ruthenium dioxide coated ruthenium supported carbon nanoplatelets prepared according to example 3 of the present invention;
FIG. 12 (a) is a low power transmission electron microscope image of the nano-sized ruthenium dioxide coated ruthenium carbon-loaded nanosheet prepared in example 4 of the present invention; (b) is a high-power transmission electron microscope image of the nano ruthenium dioxide coated ruthenium carbon-loaded micron sheet prepared in the embodiment 3 of the invention;
FIG. 13 is an XRD pattern of the nanoscale ruthenium dioxide coated ruthenium supported carbon nanoplatelets prepared in example 4 according to the present invention;
FIG. 14 (a) is a low power transmission electron microscope image of the nano-sized ruthenium dioxide coated ruthenium carbon-loaded nanosheet prepared in example 5 of the present invention; (b) is a high-power transmission electron microscope image of the nano-scale ruthenium dioxide coated ruthenium carbon-loaded micron sheet prepared in the embodiment 5 of the invention;
FIG. 15 is an XRD pattern of the nano-sized ruthenium dioxide coated ruthenium supported carbon nanoplatelets prepared according to example 5 of the present invention;
FIG. 16 (a) is a low power transmission electron microscope image of the nano-sized ruthenium dioxide coated ruthenium carbon micro-flake prepared in example 6 of the present invention; (b) is a high-power transmission electron microscope image of the nano-scale ruthenium dioxide coated ruthenium carbon-loaded micron sheet prepared in the embodiment 6 of the invention;
FIG. 17 is an XRD pattern of a nano-sized ruthenium dioxide coated ruthenium carbon-supported nanoplatelet prepared according to example 6 of the present invention;
FIG. 18 (a) is a low power transmission electron microscope image of the nano-sized ruthenium dioxide coated ruthenium supported carbon nanosheet prepared in example 7 of the present invention; (b) is a high-power transmission electron microscope image of the nano-scale ruthenium dioxide coated ruthenium carbon-loaded micron sheet prepared in example 7 of the invention;
FIG. 19 is an XRD pattern of a nanoscaled ruthenium dioxide coated ruthenium carbon nanoplatelets prepared according to example 7 of the present invention;
FIG. 20 is a schematic low power transmission electron microscope image of (a) the nanoscale ruthenium dioxide-coated ruthenium-supported carbon nanoplatelets prepared in example 8 according to the present invention; (b) is a high-power transmission electron microscope image of the nano ruthenium dioxide coated ruthenium carbon-loaded micron sheet prepared in the embodiment 8 of the invention;
FIG. 21 is an XRD pattern of a nano-sized ruthenium dioxide coated ruthenium carbon-supported nanoplatelet prepared according to example 8 of the present invention;
FIG. 22(a) is a graph showing the oxygen evolution performance of the nanosized ruthenium dioxide coated ruthenium supported carbon nanoplatelets prepared in example 8 according to the present invention; (b) a hydrogen evolution performance diagram of the nano-scale ruthenium dioxide coated ruthenium loaded carbon micron sheet prepared in the embodiment 8 of the invention; (c) is a full-hydrolysis performance diagram of the nano-scale ruthenium dioxide coated ruthenium carbon-loaded micron sheet prepared in the embodiment 8 of the invention;
FIG. 23 (a) is a low power transmission electron microscope image of the nano-sized ruthenium dioxide coated ruthenium supported carbon micro-sheet prepared in example 9 of the present invention; (b) is a high-power transmission electron microscope image of the nano-scale ruthenium dioxide coated ruthenium carbon-loaded micron sheet prepared in example 9 of the invention;
FIG. 24 is an XRD pattern of the nanoscale ruthenium dioxide coated ruthenium supported carbon nanoplatelets prepared in accordance with example 9 of the present invention;
fig. 25(a) is a graph of the oxygen evolution performance of the nanoscale ruthenium dioxide coated ruthenium supported carbon micron sheet prepared in example 9 of the present invention; (b) is a hydrogen evolution performance diagram of the nano-scale ruthenium dioxide coated ruthenium carbon micron sheet prepared in the embodiment 9 of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a nanoscale ruthenium dioxide coated ruthenium loaded carbon micron sheet, which comprises the following steps: s1) dispersing ruthenium salt and an organic carbon source in an alcohol solvent, mixing, and performing solid-liquid separation to obtain a precursor; the organic carbon source contains nitrogen; or mixing and grinding ruthenium salt and an organic carbon source to obtain a precursor; s2) carrying out high-temperature calcination on the precursor in a reducing atmosphere to obtain an intermediate product; s3) calcining the intermediate product at low temperature in air atmosphere to obtain the nano ruthenium dioxide coated ruthenium loaded carbon micron sheet.
The nanoscale ruthenium dioxide coated ruthenium loaded carbon micron sheet provided by the invention can be prepared only by simple adsorption, high-temperature calcination and low-temperature air annealing, the synthetic method is relatively simple, the raw materials are easy to obtain, the practicability is high, and the nanoscale ruthenium dioxide coated ruthenium loaded carbon micron sheet serving as a full-electrolysis water electrode material has excellent hydrogen production, oxygen production and full-electrolysis performance in a wide pH range.
In the present invention, the sources of all raw materials are not particularly limited, and they may be commercially available.
Dispersing ruthenium salt and an organic carbon source in an alcohol solvent; the ruthenium salt is preferably inorganic ruthenium salt, and more preferably ruthenium trichloride and/or ruthenium trichloride hydrate; the organic carbon source is preferably a nitrogen-containing organic carbon source, and is more preferably one or more of melamine, dicyandiamide and hexamethylenetetramine; the molar ratio of the ruthenium salt to the organic carbon source is preferably 1: (10-300), more preferably 1: (10-150), more preferably 1: (10-100), more preferably 1: (10-60), and most preferably 1: (15-60); the alcohol solvent is preferably ethanol.
Then mixing; the mixing method is preferably stirring; the mixing time is preferably 10-60 min, more preferably 20-60 min, and still more preferably 30-60 min.
After mixing, carrying out solid-liquid separation; the solid-liquid separation method is preferably centrifugation; the centrifugation speed is preferably 5000-10000 rpm, more preferably 6000-9000 rpm, more preferably 7000-9000 rpm, and most preferably 8000 rpm; the time for centrifugation is preferably 1-5 min, more preferably 1-3 min, and further preferably 2-3 min.
After solid-liquid separation, preferably drying to obtain a precursor; the drying temperature is preferably 60-80 ℃; the drying time is preferably 10-15 h, and more preferably 12-13 h.
In the invention, ruthenium salt and an organic carbon source can be mixed and ground to obtain a precursor; the types and the proportions of the ruthenium salt and the organic carbon source are the same as those described above, and are not described again; the mixing and grinding time is preferably 10-60 min, more preferably 15-40 min, and still more preferably 15-30 min.
Calcining the precursor at high temperature in a reducing atmosphere to obtain an intermediate product; the reducing atmosphere is preferably argon-hydrogen mixed atmosphere; the volume percentage content of hydrogen in the reducing atmosphere is 5-15%, more preferably 8-12%, and most preferably 10%; the high temperature calcination is preferably carried out in a tube furnace; the heating rate of the high-temperature calcination is preferably 2-10 ℃/min, and more preferably 2-5 ℃/min; the high-temperature calcination temperature is preferably 600-900 ℃; in some embodiments provided herein, the temperature of the high temperature calcination is preferably 850 ℃; in some embodiments provided herein, the temperature of the high temperature calcination is preferably 600 ℃; in some embodiments provided herein, the temperature of the high temperature calcination is preferably 900 ℃; in other embodiments provided herein, the temperature of the high temperature calcination is preferably 700 ℃; the time (namely the heat preservation time) of the high-temperature calcination is preferably 1-3 h, more preferably 1.5-2.5 h, and still more preferably 2 h; after high-temperature calcination, the mixture is preferably naturally cooled to room temperature to obtain an intermediate product.
Calcining the intermediate product at low temperature in an air atmosphere; the low temperature calcination is preferably carried out in a muffle furnace; the heating rate of the low-temperature calcination is preferably 2-5 ℃/min, and more preferably 2-3 ℃/min; the temperature of the low-temperature calcination is preferably 150-320 ℃, more preferably 200-320 ℃, and further preferably 200 ℃; the time of the low-temperature calcination is preferably 1-4 h, more preferably 1-3.5 h, and still more preferably 1-3 h; preferably cooling to room temperature after low-temperature calcination to obtain the nano ruthenium dioxide coated ruthenium loaded carbon micron sheet.
The nano ruthenium dioxide coated ruthenium loaded carbon micron sheet prepared by the invention has the characteristics of high loading capacity and high dispersion, and has large specific surface area and a large amount of mesoporous structures, the conductivity of the material is improved by chemically coupling the tiny ruthenium dioxide coated ruthenium nanoparticles and carbon, the electronic structure of the material is improved by improving the loading capacity of the ruthenium dioxide coated ruthenium nanoparticles, the number of active sites is increased, and meanwhile, the existence of the large specific surface area and the large amount of mesoporous structures is beneficial to electrolyte permeation and gas release, and the electrocatalytic activity and stability of the material are synergistically improved; the preparation method is simple, consists of simple adsorption, calcination and oxidation, and is strong in operability and easy to repeat.
The invention also provides the nano ruthenium dioxide coated ruthenium loaded carbon micron sheet prepared by the method, the nano ruthenium dioxide coated ruthenium loaded carbon micron sheet is of a porous micron sheet structure consisting of nano ruthenium dioxide coated ruthenium, and carbon elements and nitrogen elements are distributed on the micron sheet.
The main component of the nanometer ruthenium dioxide coated ruthenium loaded carbon micron sheet provided by the invention is ruthenium dioxide; the average size of the ruthenium dioxide is preferably 4-6 nm, more preferably 5-6 nm, and still more preferably 5.34 nm; the loading amount of the ruthenium dioxide in the nano-scale ruthenium dioxide coated ruthenium-loaded carbon micron sheet is preferably 85 wt% -95 wt%, more preferably 87 wt% -92 wt%, and even more preferably about 90 wt%.
The nanoscale ruthenium dioxide coated ruthenium-loaded carbon micron sheet is a porous micron sheet, the aperture is preferably 1-5 nm, more preferably 2-4 nm, and is preferably concentrated at 3 nm; it has a high specific surface area of 180-200 m2A preferred concentration is 190 to 200m2G, more preferably 193m2/g。
The invention also provides application of the nanometer ruthenium dioxide coated ruthenium loaded carbon micron sheet as a bifunctional full-electrolysis water catalyst.
In order to further illustrate the present invention, the following will describe in detail a nanoscale ruthenium dioxide coated ruthenium-supported carbon micron sheet, its preparation method and application in combination with the examples.
The reagents used in the following examples are all commercially available.
Example 1
The ruthenium source is ruthenium trichloride, the organic carbon source is melamine, and the molar ratio is 1:15.
(1) Dispersing ruthenium trichloride and melamine in ethanol according to a molar ratio of 1:15, stirring for 30min, centrifuging at 8000rpm for 2min, and drying at 60 ℃ overnight to obtain a precursor.
(2) And (3) placing the precursor in the step (1) in a tube furnace, heating to 850 ℃ at the speed of 2 ℃/min in argon-hydrogen mixed atmosphere with the volume content of 10% of hydrogen, keeping for 2h, and naturally cooling to room temperature to obtain an intermediate product.
(3) Placing the intermediate product obtained in the step (2) in a muffle furnace, raising the temperature to 200 ℃ at the speed of 2 ℃/min, keeping the temperature for 3 hours, and then naturally cooling to room temperature to obtain a final product: the ruthenium-loaded carbon nanosheet is coated with the nanoscale ruthenium dioxide.
The nano-scale ruthenium dioxide coated ruthenium carbon-supported nanoplatelets obtained in example 1 were analyzed by an X-ray diffractometer, and the XRD spectrogram thereof was as shown in fig. 1 (a).
The nano-scale ruthenium dioxide coated ruthenium carbon-loaded nanosheet obtained in example 1 was analyzed by a raman spectrometer, and the raman spectrum thereof was shown in fig. 1 (b).
The thermogravimetric graph of the nano-sized ruthenium dioxide-coated ruthenium-supported carbon nanosheet obtained in example 1 was obtained by analyzing the carbon nanosheet with a differential thermal scanner and is shown in fig. 1 (c).
The nanoscale ruthenium dioxide coated ruthenium carbon-loaded nanosheets obtained in example 1 were analyzed with a fully automatic specific surface area analyzer, and the adsorption/desorption curves thereof are shown in fig. 1 (d).
As can be seen from FIG. 1, the synthesized material is a composite of ruthenium dioxide coated ruthenium nanoparticles and carbon, and has a large specific surface area (193 m)2The/g) is more, the aperture is mainly concentrated at 3nm, and the loading capacity of ruthenium dioxide is 90 wt%.
The nano-sized ruthenium dioxide coated ruthenium carbon-loaded nanosheets obtained in example 1 were analyzed by a scanning electron microscope and a transmission electron microscope, and scanning and transmission electron microscope images thereof are shown in fig. 2(a) to (e). Wherein, FIG. 2(a) is a scanning electron microscope image; FIGS. 2(b) and (c) are low and high power transmission electron micrographs; FIG. 2(d) is a scanning transmission electron micrograph of spherical aberration correction; fig. 2(e) is an energy spectrum of a high angle annular dark field image and the corresponding C, N, O, Ru element.
It can be seen from fig. 2 that the synthesized material is a loose and porous micron sheet structure composed of nanoparticles, the nanoparticles are ruthenium dioxide coated ruthenium, carbon and nitrogen elements are distributed on the whole sheet, and oxygen and ruthenium elements are mainly concentrated on the nanoparticles.
The nano-sized ruthenium dioxide coated ruthenium carbon micron sheet obtained in example 1 was analyzed to obtain a particle size distribution diagram, as shown in fig. 3. As shown in FIG. 3, the ruthenium dioxide-coated ruthenium nanoparticles have a size distribution of 2-10 nm and an average particle diameter of 5.43 nm.
The hydrogen and oxygen production performance adopts a three-electrode system, a working electrode adopts a glassy carbon electrode with the diameter of 3mm, a counter electrode adopts a graphite rod electrode, a reference electrode adopts a saturated silver chloride electrode or a mercury oxide electrode, and the electrolyte is 0.5M H2SO4Or 0.05M H2SO4When the electrolyte is 1.0M KOH, the reference electrode of mercury oxide is used, the sweep rate of the polarization curve is 5mV/s, and the current density is 10mA/cm during the time potential test2。
The full water-resolving performance adopts a two-electrode system, and the electrolyte is respectively 0.5M H2SO4，0.05M H2SO4And 1.0M KOH, polarization curve sweep rate of 5 mV/s.
FIG. 4 is a graph showing the hydrogen generation performance of the objective product obtained in example 1, and it can be seen from FIG. 4 that the objective product has excellent hydrogen generation performance and stability in both alkaline and acidic conditions, and the current density is 10mA/cm in 1.0M KOH2The overpotential of the time is only 7mV, and the Tafel slope is 16.5 mV/dec; at 0.5M H2SO4In the range of 10mA/cm in current density2The overpotential of time was only 46mV, the Tafel slope was 56.5mV/dec, and the polarization curves were not substantially too different after ten thousand cycles in alkalinity and acidity, respectively.
FIG. 5 is a graph showing the oxygen evolution performance of the objective product obtained in example 1, and it can be seen from FIG. 5 that it has excellent oxygen evolution performance and stability in both alkaline and acidic environments and has a current density of 10mA/cm in 1.0M KOH2The overpotential of the time is only 201mV, the Tafel slope is 44.8mV/dec, 10mA/cm2The constant current test shows that the potential is only increased by 13mV after 15 hours, and the cycle stability test shows that the potential is 10mA/cm after ten thousand circles2The overpotential of (a) is shifted positively by 8 mV; and at 0.5M H2SO4In the range of 10mA/cm2The overpotential of time is only 177mV, the Tafel slope is 45.6mV/dec, the potential after 15h constant current test is only increased by 16mV, and the current density is 10mA/cm after ten thousand cycles2The overpotential of time is only 187 mV; at 0.05M H2SO4In the middle, the overpotential only needs 192mV to lead the current density to reach 10mA/cm2The Tafel slope is only 52.1mV/dec, the overpotential is almost unchanged after long-time constant current test, and the overpotential is 10mA/cm after ten thousand-turn cycle test2The overpotential in time increased by only 5 mV.
FIG. 6 shows the target product obtained in example 1The total hydrolysis performance of the product is shown in the figure, which is 1.0M KOH, 0.5M H2SO4，0.05M H2SO4To reach 10mA/cm2The overpotential of the current density is 207mV, 237mV and 239mV respectively, and constant current tests show that the overpotential has better stability in acidity and alkalinity.
FIG. 7 is a photograph showing the total hydrolysis of the objective product obtained in example 1 driven by a 1.5V cell, from which it can be seen that the total hydrolysis is driven by a 1.5V cell at 1.0M KOH, 0.5M H2SO4，0.05M H2SO4The generation of bubbles was clearly seen in all the photographs, where hydrogen was on the left and oxygen was on the right.
Example 2
The preparation was carried out in the same manner as in example 1 except that the heat treatment time in the muffle furnace was changed to 1 hour.
The nano-scale ruthenium dioxide coated ruthenium carbon-loaded nanoplatelets obtained in example 2 were analyzed by transmission electron microscopy, and the transmission electron microscopy image thereof was shown in fig. 8. It can be seen from fig. 8 that the synthesized material is a loose porous micro-sheet structure composed of nanoparticles.
The nano-scale ruthenium dioxide coated ruthenium carbon-supported nanoplatelets obtained in example 2 were analyzed by an X-ray diffractometer, and the XRD pattern thereof was obtained as shown in fig. 9. As can be seen from fig. 9, characteristic diffraction peaks of ruthenium dioxide and ruthenium were present at the same time.
Example 3
The preparation was identical to example 1, except that the thermal ramp rate in the muffle furnace was changed to 5 ℃/min.
The nano-sized ruthenium dioxide coated ruthenium carbon-loaded nanosheets obtained in example 3 were analyzed by transmission electron microscopy, and a transmission electron microscopy image thereof is shown in fig. 10. It can be seen from fig. 10 that the synthesized material is a loose porous micro-sheet structure composed of nanoparticles.
The nanoscale ruthenium dioxide-coated ruthenium-supported carbon nanoplatelets obtained in example 3 were analyzed by X-ray diffraction, and the XRD patterns thereof were obtained as shown in fig. 11. As can be seen from fig. 11, characteristic diffraction peaks of both ruthenium dioxide and ruthenium were present.
Example 4
The preparation is as in example 1, except that2The heat treatment temperature in (1) was changed to 600 ℃.
The nano-scale ruthenium dioxide coated ruthenium carbon-loaded nanoplatelets obtained in example 4 were analyzed by transmission electron microscopy, and the transmission electron microscopy image thereof was shown in fig. 12. It can be seen from fig. 12 that the synthesized material is a loose porous micro-sheet structure composed of nanoparticles.
The nanoscale ruthenium dioxide-coated ruthenium-supported carbon nanoplatelets obtained in example 4 were analyzed by X-ray diffraction, and the XRD patterns thereof were obtained as shown in fig. 13. As can be seen from fig. 13, characteristic diffraction peaks of both ruthenium dioxide and ruthenium are present.
Example 5
The preparation is identical to example 1, except that2The heat treatment temperature in (1) was changed to 900 ℃.
The nano-sized ruthenium dioxide coated ruthenium-loaded carbon nanoplatelets obtained in example 5 were analyzed by transmission electron microscopy, and the transmission electron microscopy image thereof was shown in fig. 14. It can be seen from fig. 14 that the synthesized material is a loose porous micro-sheet structure composed of nanoparticles.
The nanoscale ruthenium dioxide coated carbon micron sheet obtained in example 5 was analyzed by X-ray diffraction, and the XRD pattern thereof was obtained, as shown in fig. 15, and clearly had diffraction peaks of ruthenium dioxide and ruthenium.
Example 6
The preparation is as in example 1, except that2The thermal heating rate in (1) is changed to 10 ℃/min.
The nano-sized ruthenium dioxide coated ruthenium carbon-loaded nanosheets obtained in example 6 were analyzed by transmission electron microscopy, and a transmission electron microscopy image thereof is shown in fig. 16. It can be seen from fig. 16 that the synthesized material is a loose porous micro-sheet structure composed of nanoparticles.
The XRD patterns obtained by analyzing the nano-scale ruthenium dioxide coated ruthenium carbon-supported nanosheets obtained in example 6 by X-ray diffraction are as shown in fig. 17, and the diffraction peaks of both ruthenium dioxide and ruthenium are clearly present.
Example 7
The preparation was carried out in the same manner as in example 1, except that the stirring time was extended to 1 hour.
The nano-sized ruthenium dioxide-coated ruthenium-loaded carbon nanoplatelets obtained in example 7 were analyzed by transmission electron microscopy, and a transmission electron microscopy image thereof was obtained as shown in fig. 18. It can be seen from fig. 18 that the synthesized material is a loose porous micro-sheet structure composed of nanoparticles.
The nanoscale ruthenium dioxide-coated ruthenium-supported carbon nanoplatelets obtained in example 7 were analyzed by X-ray diffraction to obtain XRD patterns thereof, and as shown in fig. 19, diffraction peaks of both ruthenium dioxide and ruthenium were clearly present.
Example 8
The ruthenium source is ruthenium trichloride, the organic carbon source is dicyandiamide, and the molar ratio is 1:60.
(1) Mixing ruthenium trichloride and dicyandiamide according to a molar ratio of 1:60, and grinding for 15min to obtain a precursor.
(2) And (3) placing the precursor in the step (1) in a tube furnace, heating to 700 ℃ at the speed of 2 ℃/min in argon-hydrogen mixed atmosphere with the volume content of 10% of hydrogen, keeping for 2h, and naturally cooling to room temperature to obtain an intermediate product.
(3) Placing the intermediate product obtained in the step (2) in a muffle furnace, raising the temperature to 320 ℃ at the speed of 2 ℃/min, keeping the temperature for 3 hours, and then naturally cooling to room temperature to obtain a final product: the ruthenium-loaded carbon nanosheets are coated with the nanoscale ruthenium dioxide.
The nano-sized ruthenium dioxide coated ruthenium carbon-loaded nanoplatelets obtained in example 8 were analyzed by transmission electron microscopy, and the transmission electron microscopy images thereof are shown in fig. 20. It can be seen from fig. 20 that the synthesized material is a loose porous micro-sheet structure composed of nanoparticles.
The nanoscale ruthenium dioxide coated ruthenium carbon-supported nanosheet obtained in example 8 was analyzed by X-ray diffraction, and an XRD pattern thereof was obtained, as shown in fig. 21, characteristic diffraction peaks belonging to both ruthenium dioxide and ruthenium were clearly present.
FIG. 22(a) is a graph showing the oxygen evolution performance of the objective product obtained in example 8, which shows that the objective product has excellent oxygen evolution performance in both alkaline and acidic conditions, and that the objective product has a high current density in 1.0M KOHThe degree is 10mA/cm2The overpotential is only 226 mV; at 0.5M H2SO4In the range of 10mA/cm2The overpotential at this time was only 202 mV. FIG. 22(b) is a graph showing the hydrogen-producing performance of the objective product obtained in example 7, and it is understood from the graph that the hydrogen-producing activity is excellent in both the alkaline and acidic states and that the current density is 10mA/cm in 1.0M KOH2The overpotential of the time is only 29 mV; at 0.5M H2SO4In the range of 10mA/cm in current density2The overpotential at this time was only 118 mV. FIG. 22(c) is a graph showing the full hydrolytic performance of the objective product obtained in example 7, which shows that the objective product has excellent full hydrolytic performance in both alkaline and acidic environments, and the current density is 10mA/cm in 1.0M KOH2The overpotential of time is only 266 mV; at 0.5M H2SO4In the range of 10mA/cm in current density2The overpotential in this case is only 303 mV.
Example 9
The ruthenium source is ruthenium trichloride, the organic carbon source is hexamethylenetetramine, and the molar ratio is 1:60.
(1) Mixing ruthenium trichloride and hexamethylenetetramine in a molar ratio of 1:60, and grinding for 30min to obtain a precursor.
(2) And (2) placing the precursor in the step (1) into a tube furnace, heating to 700 ℃ at the speed of 2 ℃/min in an argon-hydrogen mixed atmosphere with the hydrogen volume content of 10%, keeping for 2h, and naturally cooling to room temperature to obtain an intermediate product.
(3) Placing the intermediate product obtained in the step (2) in a muffle furnace, raising the temperature to 300 ℃ at the speed of 2 ℃/min, keeping the temperature for 3 hours, and then naturally cooling to room temperature to obtain a final product: the ruthenium-loaded carbon nanosheets are coated with the nanoscale ruthenium dioxide.
The nano-sized ruthenium dioxide coated ruthenium carbon-loaded nanoplatelets obtained in example 9 were analyzed by transmission electron microscopy, and a transmission electron microscopy image thereof is shown in fig. 23. It can be seen from fig. 23 that the synthesized material is a loose porous micro-sheet structure composed of nanoparticles.
The nanoscale ruthenium dioxide-coated ruthenium-supported carbon nanoplatelets obtained in example 9 were analyzed by X-ray diffraction to obtain XRD patterns thereof, and as shown in fig. 24, characteristic diffraction peaks of both ruthenium dioxide and ruthenium were clearly present.
FIG. 25(a) is a graph showing the oxygen evolution performance of the target product obtained in example 9, from which it can be seen that the synthesized material was synthesized at 1.0M KOH and 0.5M H2SO4In the range of 10mA/cm2The overpotentials at this time were 283mV and 227mV, respectively. FIG. 25(b) is a graph showing the hydrogen evolution performance of the target product obtained in example 9, from which it can be seen that the synthesized material has excellent electrocatalytic properties in both acidic and basic conditions, which is 1.0M KOH, 0.5M H2SO4In the range of 10mA/cm in current density2The overpotential for this time was 43mV and 260mV, respectively.

Claims (8)

1. A preparation method of a nanoscale ruthenium dioxide coated ruthenium-loaded carbon micron sheet is characterized by comprising the following steps:
s1) dispersing ruthenium salt and an organic carbon source in an alcohol solvent, mixing, and performing solid-liquid separation to obtain a precursor; the organic carbon source contains nitrogen;
or mixing and grinding ruthenium salt and an organic carbon source to obtain a precursor;
s2) calcining the precursor at high temperature in a reducing atmosphere to obtain an intermediate product;
s3) calcining the intermediate product at low temperature in air atmosphere to obtain the nano ruthenium dioxide coated ruthenium loaded carbon micron sheet;
the nanometer ruthenium dioxide coated ruthenium loaded carbon micron sheet is in a porous micron sheet structure consisting of nanometer ruthenium dioxide coated ruthenium, and carbon elements and nitrogen elements are distributed on the micron sheet;
the loading amount of the ruthenium dioxide in the nanoscale ruthenium dioxide coated ruthenium-loaded carbon micron sheet is 85-95 wt%; the nano ruthenium dioxide coated ruthenium loaded carbon micron sheet is a porous micron sheet, and the aperture is 1-5 nm; the specific surface area of the nano ruthenium dioxide coated ruthenium-loaded carbon micron sheet is 180-200 m2/g。
2. The method according to claim 1, wherein the ruthenium salt is selected from the group consisting of ruthenium trichloride; the organic carbon source is selected from one or more of melamine, dicyandiamide and hexamethylenetetramine.
3. The method according to claim 1, wherein the molar ratio of the ruthenium salt to the organic carbon source is 1: (10-60).
4. The method according to claim 1, wherein the mixing time in the step S1) is 10-60 min; the solid-liquid separation is carried out by adopting a centrifugal method; the centrifugation speed is 5000-10000 rpm; the centrifugation time is 1-5 min;
the mixing and grinding time is 10-60 min.
5. The preparation method according to claim 1, wherein the temperature rise rate of the high-temperature calcination in the step S2) is 2 to 10 ℃/min; the temperature of the high-temperature calcination is 600-900 ℃; the high-temperature calcination time is 1-3 h.
6. The preparation method according to claim 1, wherein the temperature rise rate of the low-temperature calcination in the step S3) is 2-5 ℃/min; the low-temperature calcination temperature is 200-320 ℃; and the low-temperature calcination time is 1-4 h.
7. The method of claim 1, wherein the volume content of hydrogen in the reducing atmosphere is 5% to 15%.
8. The application of the nanometer ruthenium dioxide coated ruthenium loaded carbon micron sheet prepared by the preparation method of any one of claims 1 to 7 as a bifunctional full-electrolysis water catalyst.
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