CN108654604B - Preparation method and application of nitrogen-doped carbon nanotube-ruthenium dioxide composite material - Google Patents
Preparation method and application of nitrogen-doped carbon nanotube-ruthenium dioxide composite material Download PDFInfo
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- CN108654604B CN108654604B CN201710207214.XA CN201710207214A CN108654604B CN 108654604 B CN108654604 B CN 108654604B CN 201710207214 A CN201710207214 A CN 201710207214A CN 108654604 B CN108654604 B CN 108654604B
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- VDRDGQXTSLSKKY-UHFFFAOYSA-K ruthenium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ru+3] VDRDGQXTSLSKKY-UHFFFAOYSA-K 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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Abstract
The invention discloses a preparation method of a nitrogen-doped carbon nanotube-ruthenium dioxide composite material, which comprises the following steps: 1) mixing the nitrogen-doped carbon nanotube solution with the ruthenium source solution to obtain a mixed solution, adding an alkali liquor into the mixed solution, and uniformly mixing to obtain a precursor solution with the pH of 10-12; 2) aging the precursor solution at 50-90 ℃ for 3-5 h, and then centrifugally washing to obtain a precipitate; 3) and carrying out hydrothermal reaction or calcination on the precipitate to obtain the nitrogen-doped carbon nanotube-ruthenium dioxide composite material. The nitrogen-doped carbon nanotube-ruthenium dioxide composite material prepared by the preparation method has excellent OER catalytic performance and electrical conductivity. The invention also discloses application of the composite material obtained by the preparation method in catalytic oxygen evolution reaction.
Description
Technical Field
The invention relates to the technical field of nano materials. More particularly, relates to a preparation method and application of a nitrogen-doped carbon nanotube-ruthenium dioxide composite material.
Background
The nanometer ruthenium oxide (namely, the nanometer ruthenium dioxide) is a noble metal oxide, has high specific surface capacitance, high conductivity and low resistivity, and has wide application in super capacitors, catalysts and electrochemical catalysis. In the application of the catalyst, the nanometer ruthenium oxide is proved that the (110) crystal face has better OER (oxygen evolution reaction) catalytic performance, but the application is limited due to high price, easy agglomeration and insufficient conductivity.
At present, the carbon nano tube-ruthenium oxide composite material is prepared by a plurality of technologies at home and abroad, and the carbon nano tube-ruthenium oxide composite material is prepared by an in-situ deposition method in a common preparation method. For example: the chinese patent application with publication number CN1806914A discloses a method for preparing a carbon nanotube-ruthenium oxide composite material, which comprises the following steps: adding the carbon nano tube into a ruthenium trichloride solution, carrying out ultrasonic oscillation, slowly dropwise adding hydrogen peroxide by using a trace sample injection pump at room temperature, heating for reflux reaction, filtering, washing and drying to obtain the carbon nano tube loaded hydrated nano ruthenium dioxide. The method has the disadvantages that the adopted strong oxydol oxidant has certain toxicity, is not beneficial to environmental protection, and is easy to generate virulent ruthenium tetroxide when being mixed with ruthenium trichloride, thus having certain danger. The Chinese patent application with publication number CN101122040A discloses a carbon nanotube-loaded hydrous ruthenium oxide nano-powder composite material, and the preparation method comprises the following steps: dispersing the carbon nano tube in the prepared electrodeposition solution, depositing and loading ruthenium hydroxide on the carbon nano tube by an electrodeposition method to obtain a precursor, and naturally cooling the precursor after heat treatment to obtain the carbon nano tube loaded ruthenium oxide hydrate nano powder composite material. The method has the defects of serious energy consumption and poor economical efficiency by adopting an electrodeposition method.
Therefore, it is desirable to provide a new ruthenium dioxide composite material and a preparation method thereof to solve the above technical problems.
Disclosure of Invention
The first purpose of the present invention is to provide a method for preparing a nitrogen-doped carbon nanotube-ruthenium dioxide composite material, so as to solve the technical problem that the existing ruthenium dioxide cannot be applied well due to its high price, easy agglomeration and poor conductivity.
The second objective of the invention is to provide the nitrogen-doped carbon nanotube-ruthenium dioxide composite material prepared by the preparation method of the nitrogen-doped carbon nanotube-ruthenium dioxide composite material.
The third purpose of the invention is to provide the application of the nitrogen-doped carbon nanotube-ruthenium dioxide composite material.
In order to achieve the first purpose, the invention adopts the following technical scheme:
a preparation method of a nitrogen-doped carbon nanotube-ruthenium dioxide composite material is characterized by comprising the following steps:
1) mixing the nitrogen-doped carbon nanotube solution with the ruthenium source solution to obtain a mixed solution, adding an alkali liquor into the mixed solution, and uniformly mixing to obtain a precursor solution with the pH of 10-12;
2) aging the precursor solution at 50-90 ℃ for 3-5 h, and then centrifugally washing to obtain a precipitate;
3) and carrying out hydrothermal reaction or calcination on the precipitate to obtain the nitrogen-doped carbon nanotube-ruthenium dioxide composite material.
In the preparation method of the invention, the pH value of the obtained precursor liquid is adjusted by adding alkali liquor. The morphology and the size of the ruthenium dioxide particles in the obtained composite material are very sensitive to the change of the pH value of the precursor solution. If the pH value is too high, the morphology of ruthenium dioxide in the obtained composite material is poor, the size control difficulty is high, if the pH value is too low, the reaction yield is low, and the morphology of ruthenium dioxide is poor. According to the preferred embodiment of the invention, the pH value of the precursor solution is 10-11, and at the moment, the ruthenium dioxide in the obtained composite material has regular particle morphology and good size uniformity, can be uniformly combined on the surface and inside of the nitrogen-doped carbon nanotube, and has good conductivity and OER catalytic performance; more preferably, the pH of the precursor solution is 10, in which case the aforementioned effect is optimal.
The aging conditions in the present invention also have an effect on the preparation of the composite. If the aging temperature is too high, the solvent is seriously volatilized, reflux treatment is needed, and if the aging temperature is too low, the reaction speed is slow, and the reaction period is too long. According to the preferred embodiment of the present invention, the composite effect is better when the aging temperature is 70-80 ℃, and more preferably, the effect is best when the aging temperature is 80 ℃.
According to a preferred embodiment of the present invention, in the step 1), a mass ratio of the nitrogen-doped carbon nanotubes in the nitrogen-doped carbon nanotube solution to the ruthenium source in the ruthenium source solution is 1:1 to 1: 5. Preferably, the mass ratio of the nitrogen-doped carbon nanotube to the ruthenium source is 1: 1-1: 3, the ruthenium dioxide in the prepared composite material can be uniformly combined on the surface and inside of the nitrogen-doped carbon nanotube, and the composite material has good conductivity and OER catalytic performance. More preferably, the mass ratio of the nitrogen-doped carbon nanotubes to the ruthenium source is 1: 1.
According to a preferred embodiment of the present invention, in the step 1), the alkali solution is added into the mixed solution dropwise while stirring, and the stirring rate is 100 to 600r/min, preferably 200 to 400r/min, and more preferably 300 r/min. At the moment, the uniformity of mixing can be ensured, and the nitrogen-doped carbon nanotube-ruthenium dioxide composite material with uniform size and regular appearance can be obtained more favorably.
According to the preferred embodiment of the invention, in the step 1), the method for uniformly mixing is to adopt a high-gravity rotating bed for strong mixing, wherein the feed flow rate of a peristaltic pump of the high-gravity rotating bed is 200-600 mL/min, and the rotating speed of the high-gravity rotating bed is 800-2500 r/min; preferably, the feeding flow rate of a peristaltic pump of the super-gravity rotating bed is 400-600 mL/min, and the rotating speed of the super-gravity rotating bed is 1200-1800 r/min; more preferably, the feed flow rate of the peristaltic pump of the super-gravity rotating bed is 600mL/min, and the rotating speed of the super-gravity rotating bed is 1200 r/min. At the moment, the mixing uniformity is higher, and the size and the granularity of ruthenium dioxide in the obtained nitrogen-doped carbon nanotube-ruthenium dioxide composite material are smaller and the appearance is more regular.
According to a preferred embodiment of the present invention, in the step 3), the temperature of the hydrothermal reaction is 100 to 230 ℃ and the time is 4 to 24 hours. In the preparation method of the composite material, the bonding strength between the ruthenium dioxide and the nitrogen-doped carbon nanotube in the prepared composite material is sensitive to the temperature and the time of the hydrothermal reaction, the morphology regularity and the particle size uniformity of the composite material are affected by overhigh or overlow temperature and overlong or overlong time of the hydrothermal reaction, and the OER catalytic performance of the obtained composite material is poor or even has no OER catalytic performance due to overlow temperature. Preferably, the temperature of the hydrothermal reaction is 200-230 ℃ and the time is 8-12 h, and the composite material obtained at the moment has good OER catalytic performance. More preferably, the temperature of the hydrothermal reaction is 230 ℃ and the time is 12 h. The OER catalytic performance of the material obtained here is the best.
According to a preferred embodiment of the invention, in step 3), the calcination is carried out in an inert gas atmosphere, preferably nitrogen. Calcining the mixture in inert atmosphere to prepare the nitrogen-doped carbon nanotube-ruthenium dioxide composite material with regular appearance.
According to a preferred embodiment of the invention, in the step 3), the calcination temperature is 300-500 ℃ and the calcination time is 12-36 h. Preferably 18-24 h. In the process of obtaining the composite material by adopting a calcination mode, the morphology and the OER catalytic performance of the composite material are sensitive to the change of calcination conditions. Under the preferable condition, the nitrogen-doped carbon nano tube and the ruthenium dioxide in the obtained composite material are uniformly dispersed, and meanwhile, the composite material has good OER catalytic performance and electrical conductivity. Too long or too short calcination time will degrade OER catalytic performance. More preferably, the calcination temperature is 300 ℃ and the calcination time is 24h, and the OER catalytic performance of the composite material is optimal.
According to a preferred embodiment of the present invention, in step 1), the ruthenium source in the ruthenium source solution is selected from one or a mixture of ruthenium chloride, hexaammonium ruthenium trichloride and ruthenium nitrosyl nitrate. Among them, ruthenium chloride may be, for example, ruthenium trichloride.
According to a preferred embodiment of the present invention, in step 1), the alkali in the alkali solution is selected from one or more of sodium hydroxide, sodium carbonate and ammonia water.
According to a preferred embodiment of the present invention, in step 1), the ruthenium source solution and the solvent in the base are respectively and independently selected from one or two of water and ethanol.
The nitrogen-doped carbon nanotubes of the present invention can be obtained by conventional commercial methods. According to the invention, on the premise of not adding additives such as an oxidant and the like, the nitrogen-doped carbon nanotube and ruthenium dioxide are compounded, and the selection of each step of the compounding condition and the regulation and control of process parameters are adopted, so that the morphology, the size and the dispersity of the nitrogen-doped carbon nanotube-ruthenium dioxide particles are more controllable, the conversion rate and the selectivity of the reaction are greatly improved, and the process and the flow are simplified. In the preparation method of the invention, the regulation and control of the process parameters are mainly embodied as follows: the preparation process of the nitrogen-doped carbon nanotube-ruthenium dioxide comprises a series of process procedures of mixing reaction, precursor post-treatment, filtration, washing, drying, calcination/hydrothermal treatment and the like. The mutual correlation among the steps, parameters and the like is realized under the combined action, so that the problems of the morphology, the size, the dispersibility and the like of the nitrogen-doped carbon nanotube-ruthenium oxide particles are solved, the ruthenium dioxide particles are uniformly and firmly combined on the surface and inside of the nitrogen-doped carbon nanotube, the conductivity of the ruthenium dioxide is improved on one hand, and the composite material has better OER catalytic performance compared with pure ruthenium dioxide on the other hand. Endows the product with higher application performance and wider application range. Lays a good foundation for the application of the catalyst in the field of catalysts. Therefore, in order to obtain a nitrogen-doped carbon nanotube-ruthenium oxide composite material with good OER catalytic performance, the above conditions need to be strictly controlled, and any one of the conditions cannot be changed. Due to the regulation and the coordination of the process parameters, the particle size of the nanometer ruthenium dioxide product in the finally obtained composite material can be regulated and controlled between 1 nm and 20nm, the nanometer ruthenium dioxide product is uniformly dispersed on the surface and inside the nitrogen-doped carbon nanotube, and the composite material has better OER catalytic performance and conductivity.
In order to achieve the second objective, the present invention provides the nitrogen-doped carbon nanotube-ruthenium dioxide composite material prepared by the preparation method of the nitrogen-doped carbon nanotube-ruthenium dioxide composite material. The ruthenium dioxide particles in the nitrogen-doped carbon nanotube-ruthenium dioxide composite material are uniformly combined on the surface and inside the nitrogen-doped carbon nanotube; the nitrogen-doped carbon nanotube has the length of 0.5-30 mu m and the diameter of 30-50 nm, and the ruthenium oxide particles are spherical or rod-shaped structures and have the size of 1-20 nm.
In order to achieve the third purpose, the invention provides the application of the nitrogen-doped carbon nanotube-ruthenium dioxide composite material prepared by the preparation method as a catalyst in catalyzing the oxygen evolution reaction of electrolyzed water.
The nitrogen-doped carbon nanotube-ruthenium dioxide composite material prepared by the method has good application in the aspects of super capacitors and other catalysis fields.
In the present invention, all the raw materials used may be commercially available unless otherwise specified.
The invention has the following beneficial effects:
1) the nitrogen-doped carbon nanotube and ruthenium oxide composite material is prepared by adopting a supergravity method, and the using method is simple and environment-friendly; the ruthenium dioxide and the nitrogen-doped carbon nanotube are preferably compounded, wherein the length of the doped carbon nanotube is 0.5-30 mu m, the diameter of the doped carbon nanotube is 30-50 nm, the shape of the compounded nano ruthenium dioxide particle is a spherical or rod-shaped structure, the particle size can reach 1-20 nm, the nano ruthenium dioxide particle is compounded on the surface and inside of the nitrogen-doped carbon nanotube, and the composite material is better in dispersion.
2) The composite material prepared by the invention has higher OER catalytic performance and conductivity, through electrochemical performance test, the OER catalytic overpotential can reach 50mV/min or more, and the composite material has better catalytic performance compared with other ruthenium dioxide composite materials.
3) The method has the advantages of simple process flow, easy operation, easy storage of the obtained product, high product purity, good quality, strong experiment repeatability and easy amplification.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 shows a TEM image of a composite material obtained in example 1 of the present invention.
FIG. 2 shows a TEM image of a composite material obtained in example 2 of the present invention.
Fig. 3 shows the composite materials obtained in example 1, example 9 and comparative example 7 of the present invention as LSV catalytic diagrams.
FIG. 4 shows a schematic diagram of a hypergravity rotating packed bed reactor used in example 10 of the present invention.
FIG. 5 shows a schematic view of a tubular annular microchannel reactor according to example 11 of the present invention.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. Similar parts in the figures are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
A preparation method of a nitrogen-doped carbon nanotube-ruthenium dioxide composite material comprises the following steps:
1) dissolving 0.4g of hexaammonium ruthenium trichloride in 40ml of ethanol to prepare a hexaammonium ruthenium trichloride solution;
2) dissolving 0.22g of sodium hydroxide in 40ml of ethanol to prepare a sodium hydroxide solution;
3) mixing 7mL of nitrogen-doped carbon nanotube with solid content of 3 wt% with a hexaammonium trichloride ruthenium solution (the mass ratio of the nitrogen-doped carbon nanotube to the hexaammonium trichloride ruthenium is 1:2), then dropwise adding a sodium hydroxide solution, controlling the reaction temperature to be 25 ℃, stirring at a speed of 600r/min, and adjusting and controlling the final pH value of the reaction system to be 10 by using the sodium hydroxide solution;
4) after the final pH value requirement of the reaction system is met, aging for 4 hours at a constant temperature of 70 ℃;
5) and (3) centrifugally washing the aged solution, transferring the solution into a reaction kettle, and carrying out hydrothermal treatment at the hydrothermal temperature of 200 ℃ for 12 hours.
6) And drying the reaction solution after hydrothermal treatment to obtain the nitrogen-doped carbon nanotube-ruthenium dioxide composite material.
Fig. 1 is a TEM analysis diagram of the product obtained in this embodiment, and it can be seen from the diagram that the obtained nitrogen-doped carbon nanotube-ruthenium dioxide composite material is better in composite, wherein the particle size of ruthenium oxide is 3-10 nm, and the ruthenium oxide is a more regular spherical structure.
The obtained composite material is used as a catalyst to be applied to the oxygen evolution reaction of catalytic electrolysis water, and the method comprises the following steps:
the oxygen reduction and oxygen evolution catalytic activity of the catalyst was studied using a Rotating Ring Disk Electrode (RRDE) technology with an electrochemical system (AFMSRX rotating device, AFCBP1 double potentiostat, pin, usa). The electrode head consists of a glassy carbon disc electrode (diameter 5mm, geometric surface area 0.196 cm)2) And a peripheral platinum ring electrode (geometric surface area of 0.125 cm)2) And (4) forming. The electrochemical test was carried out at room temperature using a standard three-electrode system with a platinum wire as counter electrode and an Ag/AgCl electrode as reference electrode (3mol/L Cl)-)The working electrode is a Rotating Disk Electrode (RDE) provided with a glassy carbon electrode tip (the surface of the glassy carbon is covered with a catalyst), and the electrolyte is 0.1mol/L KOH solution. Sample preparation: firstly weighing 50mg of the prepared nitrogen-doped carbon nanotube-ruthenium dioxide composite material, dissolving the nitrogen-doped carbon nanotube-ruthenium dioxide composite material in 1mL of ethanol and 50 mu L of Nafion solution, carrying out ultrasonic treatment for half an hour, and then sucking 5 mu L of the nitrogen-doped carbon nanotube-ruthenium dioxide composite material solution twice by using a liquid-transfering gun and dripping the solution into a glassy carbon disc electrode. And testing by adopting an electrochemical workstation to obtain an LSV curve. From the LSV curve, it can be seen that when the current reached per square centimeter exceeds 10mA, the overpotential is 1.59V.
For comparison, the nitrogen-doped carbon nanotube-ruthenium dioxide composite material in the oxygen absorption reaction method is replaced by commercially available ruthenium dioxide, an LSV curve is measured, and when the current reaching each square centimeter exceeds 10mA, the overpotential exceeds 1.7V, namely the overpotential measuring range is exceeded.
Therefore, the prepared composite material can effectively reduce the overpotential of the oxygen evolution reaction, improve the efficiency of the electrolytic water oxygen evolution reaction, and can be better used as a catalyst for catalyzing the oxygen evolution reaction of the electrolytic water.
Example 2
A preparation method of a nitrogen-doped carbon nanotube-ruthenium dioxide composite material comprises the following steps:
1) dissolving 3g of ruthenium trichloride in 150ml of water to prepare a ruthenium trichloride solution;
2) dissolving 1.50g of sodium hydroxide in 150ml of water to prepare a sodium hydroxide solution;
3) mixing 78.75mL of nitrogen-doped carbon nanotube with the solid content of 3 wt% with a ruthenium trichloride solution (the mass ratio of the nitrogen-doped carbon nanotube to the ruthenium trichloride is 1:2), then dropwise adding a sodium hydroxide solution, controlling the reaction temperature to be 25 ℃, stirring at a rate of 500r/min, and adjusting and controlling the final pH value of the reaction system to be 10 by using the sodium hydroxide solution;
4) after the final pH value requirement of the reaction system is met, aging for 5 hours at the constant temperature of 60 ℃;
5) centrifugally washing the aged solution, then placing the washed solution into a crucible, and calcining the solution in a nitrogen atmosphere at the calcining temperature of 300 ℃ for 14 h;
6) and taking out the calcined composite material to obtain the nitrogen-doped carbon nanotube-ruthenium dioxide composite material.
Fig. 2 is a TEM analysis diagram of a product obtained in example 2 of the present invention, and it can be seen from the diagram that the obtained nitrogen-doped carbon nanotube-ruthenium dioxide composite material is better in composite, wherein the ruthenium oxide particle size in the composite material is 5-20 nm, and the composite material is a more regular spherical structure. The composite material obtained was used as a catalyst in the oxygen evolution reaction of catalytic electrolysis water as described in example 1. From the LSV curve, when the current reaching each square centimeter exceeds 10mA, the overpotential is 1.54V, namely, the composite material can effectively reduce the overpotential of the oxygen evolution reaction and can be better used as a catalyst to catalyze the oxygen evolution reaction of the electrolyzed water.
Example 3
A preparation method of a nitrogen-doped carbon nanotube-ruthenium dioxide composite material comprises the following steps:
1) dissolving 1g of ruthenium nitrosyl nitrate in 100mL of deionized water/ethanol with the ratio of 1:1, and carrying out ultrasonic treatment for 0.5 h;
2) dissolving 0.56g of sodium hydroxide in 100mL of deionized water/ethanol with the ratio of 1:1, and carrying out ultrasonic treatment for 0.5 h;
3) mixing 78.75mL of nitrogen-doped carbon nanotube solution with the solid content of 3 wt% with a nitrosyl ruthenium nitrate solution (at the moment, the mass ratio of the nitrogen-doped carbon nanotube to the nitrosyl ruthenium nitrate is 1:2), dropwise adding a sodium hydroxide solution into the mixed solution, controlling the reaction temperature to be 35 ℃, stirring at the speed of 800r/min, and adjusting and controlling the final pH value of the reaction system to be 11 by using the sodium hydroxide solution;
4) after the final pH value requirement of the reaction system is met, heating to 90 ℃, and aging for 3 h;
5) washing the aged solution by dialysis, then placing the washed solution into a crucible, and calcining the solution in a nitrogen atmosphere at the calcining temperature of 500 ℃ for 24 hours;
6) and taking out the calcined composite material to obtain the nitrogen-doped carbon nanotube-ruthenium dioxide composite material.
The obtained nitrogen-doped carbon nanotube-ruthenium dioxide composite material is better in composite, wherein the particle size of ruthenium oxide in the composite material is 10-25 nm, and the composite material is a more regular spherical structure. The composite material obtained was used as a catalyst in the oxygen evolution reaction of catalytic electrolysis water as described in example 1. From the LSV curve, when the current reaching each square centimeter exceeds 10mA, the overpotential is 1.56V, namely, the composite material can effectively reduce the overpotential of the oxygen evolution reaction and can be better used as a catalyst to catalyze the oxygen evolution reaction of the electrolyzed water.
Example 4
A preparation method of a nitrogen-doped carbon nanotube-ruthenium dioxide composite material comprises the following steps:
1) dissolving 20g of ruthenium trichloride hydrate and hexaammonium ruthenium trichloride in a ratio of 1:1 in 2000ml of deionized water to prepare a ruthenium solution;
2) preparing 5mol/L ammonia water solution, taking out 8ml of ammonia water, and adding the ammonia water into 1992ml of deionized water to prepare ammonia water solution;
3) mixing 350mL of nitrogen-doped carbon nanotube solution with the solid content of 3 wt% with ruthenium source solution (at the moment, the mass ratio of the nitrogen-doped carbon nanotube to the total amount of the ruthenium trichloride hydrate and the ruthenium hexaammonium trichloride is 1:2), then dropwise adding an ammonia water solution into the mixed solution, controlling the reaction temperature to be 25 ℃, stirring at the speed of 600r/min, and adjusting and controlling the final pH value of the reaction system to be 12 by using the ammonia water solution;
4) after the final pH value requirement of the reaction system is met, aging is carried out for 5h at 70 ℃;
5) dialyzing and washing the aged solution, and then transferring the solution to a hydrothermal reaction kettle for hydrothermal treatment, wherein the hydrothermal time is 12 hours and the hydrothermal temperature is 100 ℃;
6) and drying the solution after the water is heated to obtain the nitrogen-doped carbon nanotube-ruthenium dioxide composite material.
The obtained nitrogen-doped carbon nanotube-ruthenium dioxide composite material is better in composite, wherein the particle size of ruthenium oxide in the composite material is 1-15 nm, and the composite material is a more regular spherical structure. The composite material obtained was used as a catalyst in the oxygen evolution reaction of catalytic electrolysis water as described in example 1. From the LSV curve, it is clear that when the current reached per square centimeter exceeds 10mA, the overpotential is above 1.7V, and the composite does not reduce the overpotential of the oxygen evolution reaction.
Example 5
A preparation method of a nitrogen-doped carbon nanotube-ruthenium dioxide composite material comprises the following steps:
1) dissolving 1g of ruthenium trichloride, ruthenium nitrosyl nitrate and hexaammonium ruthenium trichloride in a ratio of 1:1:1 in 100mL of 1:2 deionized water/ethanol to prepare a ruthenium source solution;
2) dissolving 0.3g of potassium hydroxide in 100mL of 1:2 deionized water/ethanol to prepare a potassium hydroxide solution;
3) mixing 14mL of nitrogen-doped carbon nanotube solution with the solid content of 3 wt% with ruthenium source solution (the mass ratio of the nitrogen-doped carbon nanotube to the total amount of ruthenium trichloride, ruthenium nitrosyl nitrate and ruthenium hexaammonium trichloride is 1:2), dropwise adding potassium hydroxide solution into the ruthenium source solution, controlling the reaction temperature at 30 ℃, stirring at the speed of 500r/min, and adjusting and controlling the final pH value of the reaction system to be 10;
4) after the final pH value requirement of the reaction system is met, heating to 80 ℃, and aging for 3 h;
5) filtering and washing the aged solution, transferring the solution to a crucible, and calcining the crucible in an argon atmosphere for 24 hours at the calcining temperature of 300 ℃;
6) and taking out the calcined composite material to obtain the nitrogen-doped carbon nanotube-ruthenium dioxide composite material.
The obtained nitrogen-doped carbon nanotube-ruthenium dioxide composite material is better in composite, wherein the particle size of ruthenium oxide in the composite material is 1-3 nm, and the composite material is of a regular spherical structure. The composite material obtained was used as a catalyst in the oxygen evolution reaction of catalytic electrolysis water as described in example 1. The LSV curve of the resulting composite is shown as curve 5 in figure 3. The LSV test shows that when the current reaching each square centimeter exceeds 10mA, the overpotential is 1.51V, namely the overpotential for generating the oxygen evolution reaction is low, the OER catalytic performance is better, and the catalyst can be better used for catalyzing the oxygen evolution reaction of the electrolyzed water.
Example 6
A preparation method of a nitrogen-doped carbon nanotube-ruthenium dioxide composite material comprises the following steps:
1) dissolving 2g of hydrated ruthenium trichloride in 200mL of deionized water to prepare a ruthenium trichloride solution;
2) dissolving 1.5g of sodium hydroxide in 100mL of deionized water to prepare a sodium hydroxide solution;
3) mixing 70mL of nitrogen-doped carbon nanotube solution with the solid content of 3 wt% with a ruthenium trichloride solution (at the moment, the mass ratio of the nitrogen-doped carbon nanotube to the ruthenium trichloride hydrate is 1:2), dropwise adding a sodium hydroxide solution into the ruthenium trichloride solution, controlling the reaction temperature to be 50 ℃, stirring at the speed of 900r/min, and adjusting and controlling the final pH value of the reaction system to be 12 by using the sodium hydroxide solution;
4) after the final pH value requirement of the reaction system is met, heating to 80 ℃, and aging for 3 h;
5) dialyzing and washing the aged solution, and then transferring the solution to a hydrothermal reaction kettle for hydrothermal treatment, wherein the hydrothermal time is 4 hours and the hydrothermal temperature is 160 ℃;
6) and drying the solution after the water is heated to obtain the nitrogen-doped carbon nanotube-ruthenium dioxide composite material.
The obtained nitrogen-doped carbon nanotube-ruthenium dioxide composite material is better in composite, wherein the particle size of ruthenium oxide is 1-7 nm, and the ruthenium oxide is of a more regular spherical structure. The composite material obtained was used as a catalyst in the oxygen evolution reaction of catalytic electrolysis water as described in example 1. From the LSV curve, it is clear that when the current reached per square centimeter exceeds 10mA, the overpotential is above 1.7V, and the composite does not reduce the overpotential of the oxygen evolution reaction.
Example 7
A preparation method of a nitrogen-doped carbon nanotube-ruthenium dioxide composite material comprises the following steps:
1) dissolving 1.5g of hexaammonium ruthenium trichloride and ruthenium nitrosyl nitrate in a ratio of 1:1 in 105ml of water to prepare a ruthenium source solution;
2) preparing 5mol/L ammonia water solution, taking out 2mL of ammonia water, and adding the ammonia water into 118mL of deionized water;
3) mixing 21mL of nitrogen-doped carbon nanotube solution with the solid content of 3 wt% with a ruthenium trichloride solution (the total mass ratio of the nitrogen-doped carbon nanotube to ruthenium hexammoniate trichloride and ruthenium nitrosyl nitrate is 1:2), dropwise adding an ammonia water solution into a ruthenium source solution, controlling the reaction temperature to be 40 ℃, stirring at the speed of 300r/min, and adjusting and controlling the final pH value of the reaction system to be 11 by using a sodium hydroxide solution;
4) after the final pH value requirement of the reaction system is met, heating to 70 ℃, and aging for 4 h;
5) dialyzing and washing the aged solution, and then transferring the solution to a hydrothermal reaction kettle for hydrothermal treatment, wherein the hydrothermal time is 12 hours and the hydrothermal temperature is 130 ℃;
6) drying the solution after the water heating, and placing the solution in a crucible to be calcined in a nitrogen atmosphere, wherein the calcination time is 12 hours and the temperature is 300 ℃;
7) and taking out the calcined composite material to obtain the nitrogen-doped carbon nanotube-ruthenium dioxide composite material.
The obtained nitrogen-doped carbon nanotube-ruthenium dioxide composite material is better in composite, wherein the particle size of ruthenium oxide is 5-15 nm, and the ruthenium oxide is of a more regular spherical structure. The composite material obtained was used as a catalyst in the oxygen evolution reaction of catalytic electrolysis water as described in example 1. From the LSV curve, when the current reaching each square centimeter exceeds 10mA, the overpotential is 1.57V, namely, the composite material can effectively reduce the overpotential of the oxygen evolution reaction and can be better used as a catalyst to catalyze the oxygen evolution reaction of the electrolyzed water.
Example 8
A preparation method of a nitrogen-doped carbon nanotube-ruthenium dioxide composite material comprises the following steps:
1) dissolving 1g of ruthenium nitrosyl nitrate in 10mL of deionized water to prepare a ruthenium source solution;
2) dissolving 0.56g of sodium hydroxide in 40mL of deionized water to prepare a sodium hydroxide solution;
3) mixing 7mL of nitrogen-doped carbon nanotube solution with the solid content of 3 wt% with ruthenium trichloride solution (the mass ratio of the nitrogen-doped carbon nanotube to the nitrosyl ruthenium nitrate is 1:2), dropwise adding sodium hydroxide solution into ruthenium source solution, controlling the reaction temperature to be 35 ℃, stirring at the speed of 400r/min, and adjusting and controlling the final pH value of the reaction system to be 10 by using the sodium hydroxide solution;
4) after the final pH value requirement of the reaction system is met, heating to 50 ℃, and aging for 5 hours;
5) dialyzing and washing the aged solution, and then transferring the solution to a hydrothermal reaction kettle for hydrothermal treatment, wherein the hydrothermal time is 12 hours, and the calcination temperature is 230 ℃;
6) drying the solution after the water heating, and placing the solution in a crucible to be calcined in an argon atmosphere, wherein the calcination time is 12 hours and the temperature is 500 ℃;
7) and taking out the calcined composite material to obtain the nitrogen-doped carbon nanotube-ruthenium dioxide composite material.
The obtained nitrogen-doped carbon nanotube-ruthenium dioxide composite material is better in composite, wherein the particle size of ruthenium oxide is 10-25 nm, and the ruthenium oxide is of a more regular spherical structure. The composite material obtained was used as a catalyst in the oxygen evolution reaction of catalytic electrolysis water as described in example 1. From the LSV curve, when the current reaching each square centimeter exceeds 10mA, the overpotential is 1.53V, namely, the composite material can effectively reduce the overpotential of the oxygen evolution reaction and can be better used as a catalyst to catalyze the oxygen evolution reaction of the electrolyzed water.
Example 9
Example 5 was repeated except that the calcination time was changed to 12 hours and the remaining conditions were not changed to prepare a nitrogen-doped carbon nanotube-ruthenium dioxide composite. The OER catalytic performance is shown in curve 4 of FIG. 3.
Comparative example 1
A preparation method of a nitrogen-doped carbon nanotube-ruthenium dioxide composite material comprises the following steps:
1) dissolving 5g of hydrated ruthenium trichloride in 500mL of ethanol to prepare a ruthenium trichloride solution;
2) dissolving 3.5g of sodium carbonate in 500mL of ethanol to prepare a sodium carbonate solution;
3) mixing 35mL of nitrogen-doped carbon nanotube solution with the solid content of 3 wt% with a ruthenium trichloride solution (at the moment, the mass ratio of the nitrogen-doped carbon nanotube to the ruthenium trichloride hydrate is 1:2), dropwise adding a sodium carbonate solution into the ruthenium trichloride solution, controlling the reaction temperature to be 35 ℃, stirring at the speed of 600r/min, and adjusting and controlling the final pH value of the reaction system to be 7 by using the sodium carbonate solution;
4) after the final pH value requirement of the reaction system is met, heating to 90 ℃, and aging for 3 h;
5) filtering and washing the aged solution, transferring the solution to a crucible, and calcining the crucible in an argon atmosphere for 4 hours at the calcining temperature of 100 ℃;
6) and taking out the calcined composite material to obtain the nitrogen-doped carbon nanotube-ruthenium dioxide composite material.
The nitrogen-doped carbon nanotube-ruthenium dioxide composite material has high dispersity of ruthenium oxide particles with the particle size of 10-40 nm, and the composite material has poor regularity.
Comparative example 2
Example 5 is repeated, except that in step 3), the pH of the reaction system is controlled at 8, and the remaining conditions are unchanged, to prepare the nitrogen-doped carbon nanotube-ruthenium dioxide composite material. The particle size of ruthenium dioxide in the composite material reaches 5-30 nm, and the particle morphology regularity is poor. The composite material obtained was used as a catalyst in the oxygen evolution reaction of catalytic electrolysis water as described in example 1. From the LSV curve, it can be seen that when the current reached per square centimeter exceeds 10mA, the overpotential is 1.68V, i.e. the composite material has a poor ability to reduce the overpotential of the oxygen evolution reaction.
Comparative example 3
Example 5 was repeated except that in step 3), the pH of the reaction system was controlled at 13, and the remaining conditions were unchanged, to prepare the nitrogen-doped carbon nanotube-ruthenium dioxide composite. The particle size of ruthenium dioxide in the composite material reaches 3-30 nm, and the particle morphology regularity is poor. The composite material obtained was used as a catalyst in the oxygen evolution reaction of catalytic electrolysis water as described in example 1. From the LSV curve, it can be seen that when the current reached per square centimeter exceeds 10mA, the overpotential is 1.66V, i.e. the composite material has a poor ability to reduce the overpotential of the oxygen evolution reaction.
Comparative example 4
Example 5 was repeated except that in step 4), the aging temperature was changed to 40 ℃, and the remaining conditions were not changed to prepare the nitrogen-doped carbon nanotube-ruthenium dioxide composite. The particle size of ruthenium dioxide in the composite material reaches 3-32 nm, and the particle morphology regularity is poor. The composite material obtained was used as a catalyst in the oxygen evolution reaction of catalytic electrolysis water as described in example 1. From the LSV curve, it is known that when the current reached per square centimeter exceeds 10mA, the overpotential is above 1.7V, i.e. the composite material has a poor ability to reduce the overpotential of the oxygen evolution reaction.
Comparative example 5
Example 5 was repeated except that in step 5), the calcination temperature was changed to 700 ℃, and the remaining conditions were not changed to prepare the nitrogen-doped carbon nanotube-ruthenium dioxide composite. The particle size of ruthenium dioxide in the composite material reaches 12-28 nm, and the particle morphology regularity is poor.
Comparative example 6
Example 5 was repeated except that in step 5), the calcination temperature was changed to 250 ℃ and the remaining conditions were not changed to prepare the nitrogen-doped carbon nanotube-ruthenium dioxide composite. The particle size of ruthenium dioxide in the composite material reaches 8-30 nm, and the particle morphology regularity is poor. The composite material obtained was used as a catalyst in the oxygen evolution reaction of catalytic electrolysis water as described in example 1. From the LSV curve, it is known that when the current reached per square centimeter exceeds 10mA, the overpotential is above 1.7V, i.e. the composite material has a poor ability to reduce the overpotential of the oxygen evolution reaction.
Comparative example 7
The embodiment 5 is repeated, except that in the step 5), the calcination time is changed to 10h, 4h, 2h and 1h, and the other conditions are not changed, so that the nitrogen-doped carbon nanotube-ruthenium dioxide composite material is prepared. The particle size of ruthenium dioxide in the composite material reaches 8-35 nm, and the particle morphology regularity is poor. The OER catalytic performance of the composite material is shown as curves 1-3 in a graph 3. It can be seen from fig. 3 that at calcination temperatures below 12h, when the current reached per square centimeter exceeds 10mA, the overpotential is large and the composite material has a poor ability to reduce the overpotential of the oxygen evolution reaction.
Comparative example 8
Example 5 was repeated except that in step 5), the calcination time was changed to 40h, and the remaining conditions were unchanged, to prepare the nitrogen-doped carbon nanotube-ruthenium dioxide composite. The particle size of ruthenium dioxide in the composite material reaches 20-40 nm, and the particle morphology regularity is poor.
Example 10
The supergravity rotating packed bed reactor used in the present invention is a prior art, such as the one disclosed in the patent publication (ZL 95215430.7); the schematic diagram of the reactor adopting the super-gravity rotating packed bed is shown in figure 4, wherein the meanings represented by the numbers in the diagram are as follows: the device comprises a 1-ruthenium salt/nitrogen-doped carbon nanotube mixed solution feeding port, a 2-alkali liquor feeding port, a 3-filler, a 4-motor and a 5-suspension liquid outlet.
A method for preparing a nitrogen-doped carbon nanotube-ruthenium dioxide composite material by using a supergravity rotating packed bed reactor comprises the following steps:
1) dissolving 5g of ruthenium trichloride in 300mL of deionized water, adding 35mL of nitrogen-doped carbon nanotube solution with solid content of 3 wt%, and adding the mixed solution into a ruthenium salt/nitrogen-doped carbon nanotube mixed solution storage tank; adding 300ml of aqueous solution with the sodium hydroxide mass concentration of 0.5% into an alkali liquor storage tank;
2) starting the supergravity rotating device, and adjusting the rotating speed to 2500 rpm;
3) starting a feed pump, simultaneously conveying the mixed solution and the alkali liquor to a rotating bed for a precipitation crystallization reaction, controlling the feed flow ratio of the ruthenium salt solution to the alkali liquor to be 1:1, and controlling the temperature of a reaction system to be 25 ℃;
4) after the ruthenium salt solution and the alkali liquor are fed completely, the reaction liquid obtained by the reaction completely flows out of the hypergravity rotating device, and then the hypergravity rotating device is closed;
5) transferring the obtained reaction liquid into a dispersion tank, starting an ultrasonic dispersion device of the dispersion tank, and carrying out ultrasonic treatment on the reaction liquid for 4min at the reaction temperature of 70 ℃;
6) impurities are washed by dialysis, then the reaction solution is transferred to a crucible and calcined in the nitrogen atmosphere, the calcining temperature is 300 ℃, and the calcining time is 24 hours;
7) and taking out the calcined composite material to obtain the nitrogen-doped carbon nanotube-ruthenium dioxide composite material.
The obtained nitrogen-doped carbon nanotube is well compounded with the ruthenium oxide composite material, wherein the particle size of the ruthenium oxide is 10-25 nm, and the ruthenium oxide composite material is a regular spherical structure. The composite material has better OER catalytic performance. The composite material obtained was used as a catalyst in the oxygen evolution reaction of catalytic electrolysis water as described in example 1. From the LSV curve, it is known that when the current reached per square centimeter exceeds 10mA, the overpotential is lower and the composite material has the capacity to reduce the overpotential of the oxygen evolution reaction.
Example 11
The sleeve-type annular microchannel reactor used in the present invention is a prior art, such as that disclosed in patent publication (200710177291.1 or 200810116581. X). The schematic diagram of the annular microchannel reactor using the sleeve type is shown in FIG. 5. The figures represent the following meanings: 6-inner tube, 7-outer tube, 8-continuous phase outlet, 9-annular microchannel, 10-microporous membrane, 11-continuous phase inlet, 12-dispersed phase fluid inlet, and 13-flange.
A method for preparing a nitrogen-doped carbon nanotube-ruthenium dioxide composite material by using a sleeve type annular microchannel reactor comprises the following steps:
1) dissolving 2g of ruthenium nitrosyl nitrate into 100mL of 1:3 deionized water/ethanol, adding 14mL of nitrogen-doped carbon nanotube solution with the solid content of 3 wt%, and adding the mixed solution into a ruthenium source/nitrogen-doped carbon nanotube storage tank; dissolving 1.12g of sodium hydroxide in 100mL of 1:3 deionized water/ethanol, and adding the solution into an alkali liquor storage tank;
2) controlling the temperature of the reaction system to be 25 ℃; starting a feeding pump, simultaneously conveying the mixed solution and the alkali liquor to a sleeve type annular micro-channel reactor for precipitation crystallization reaction, and controlling the feeding flow rates of the ruthenium salt solution and the alkali liquor to be 2L/min and 2L/min respectively;
3) transferring the obtained reaction liquid into a dispersion tank, starting an ultrasonic dispersion device of the dispersion tank, and carrying out ultrasonic treatment on the reaction liquid for 3 hours at the ultrasonic temperature of 80 ℃;
4) centrifugally washing impurities, transferring the reaction solution to a crucible, and calcining in a nitrogen atmosphere at 500 ℃ for 24 hours;
5) and taking out the calcined composite material to obtain the nitrogen-doped carbon nanotube-ruthenium dioxide composite material.
The obtained nitrogen-doped carbon nanotube is well compounded with the ruthenium oxide composite material, wherein the particle size of the ruthenium oxide is 15-25 nm, and the ruthenium oxide composite material is of a regular spherical structure. The composite material obtained was used as a catalyst in the oxygen evolution reaction of catalytic electrolysis water as described in example 1. From the LSV curve, it is known that when the current reached per square centimeter exceeds 10mA, the overpotential is lower and the composite material has the capacity to reduce the overpotential of the oxygen evolution reaction.
Example 12
Example 10 was repeated except that the molecular mixing enhanced reactor used was one of a high gravity reactor, a rotary reactor, a stator-rotor reactor, a static mixing reactor, a Y-type microchannel reactor, and a T-type microchannel reactor, and the rest of the process conditions were similar; the effect thereof is similar to that of example 10.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (16)
1. A preparation method of a nitrogen-doped carbon nanotube-ruthenium dioxide composite material is characterized by comprising the following steps:
1) mixing the nitrogen-doped carbon nanotube solution with the ruthenium source solution to obtain a mixed solution, adding an alkali liquor into the mixed solution, and uniformly mixing to obtain a precursor solution with the pH of 10-12;
2) aging the precursor solution at 50-90 ℃ for 3-5 h, and then centrifugally washing to obtain a precipitate;
3) carrying out hydrothermal reaction or calcination on the precipitate to obtain the nitrogen-doped carbon nanotube-ruthenium dioxide composite material; wherein the temperature of the hydrothermal reaction is 100-230 ℃ and the time is 4-24 h.
2. The method according to claim 1, wherein in the step 1), the mass ratio of the nitrogen-doped carbon nanotube to the ruthenium source in the mixed solution is 1:1 to 1: 5.
3. The method according to claim 1, wherein in the step 1), the mass ratio of the nitrogen-doped carbon nanotube to the ruthenium source in the mixed solution is 1:1 to 1: 3.
4. The method according to claim 1, wherein in step 1), the mass ratio of the nitrogen-doped carbon nanotubes to the ruthenium source in the mixed solution is 1: 1.
5. The method according to claim 1, wherein the pH of the precursor solution in step 1) is 10 to 11.
6. The method according to claim 1, wherein the precursor solution has a pH of 10 in step 1).
7. The preparation method of claim 1, wherein in the step 1), the alkali solution is added into the mixed solution dropwise while stirring, and the stirring rate is 100-600 r/min; or the uniformly mixing method adopts a high-gravity rotating bed to perform strong mixing, the feed flow of a peristaltic pump of the high-gravity rotating bed is 200-600 mL/min, and the rotating speed of the high-gravity rotating bed is 800-2500 r/min.
8. The method according to claim 1, wherein the aging temperature in the step 2) is 70 to 80 ℃.
9. The method according to claim 1, wherein the aging temperature in the step 2) is 80 ℃.
10. The preparation method according to claim 1, wherein in the step 3), the temperature of the hydrothermal reaction is 200-230 ℃ and the time is 8-12 h.
11. The preparation method according to claim 1, wherein the hydrothermal reaction in step 3) is carried out at 230 ℃ for 12 hours.
12. The production method according to claim 1, wherein in step 3), the calcination is performed in an inert gas atmosphere or a nitrogen atmosphere; the calcining temperature is 300-500 ℃, and the calcining time is 12-36 h.
13. The preparation method according to claim 1, wherein in the step 3), the calcination temperature is 300 ℃ and the calcination time is 24 h.
14. The preparation method according to claim 1, wherein in step 1), the ruthenium source in the ruthenium source solution is selected from one or more of ruthenium chloride, hexaammonium ruthenium trichloride and ruthenium nitrosyl nitrate; the alkali in the alkali liquor is selected from one or a mixture of sodium hydroxide, sodium carbonate and ammonia water; the ruthenium source solution and the solvent in the alkali liquor are respectively and independently selected from one or two of water and ethanol.
15. The N-doped carbon nanotube-ruthenium dioxide composite material prepared by the preparation method according to any one of claims 1 to 14, wherein the ruthenium dioxide particles in the N-doped carbon nanotube-ruthenium dioxide composite material are uniformly bonded on the surface and inside of the N-doped carbon nanotube; the nitrogen-doped carbon nanotube has the length of 0.5-30 mu m and the diameter of 30-50 nm, and the ruthenium oxide particles are spherical or rod-shaped structures and have the size of 1-20 nm.
16. The nitrogen-doped carbon nanotube-ruthenium dioxide composite material prepared by the preparation method of any one of claims 1 to 14 is applied to catalyzing oxygen evolution reaction of electrolyzed water as a catalyst.
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| CN111628187A (en) * | 2020-05-05 | 2020-09-04 | 江苏大学 | Carbon-supported ruthenium oxide catalyst and preparation method thereof |
| CN112680741B (en) * | 2021-01-12 | 2022-03-22 | 江苏大学 | Preparation method and application of ruthenium-doped cobalt phosphide electrocatalyst |
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