CN111215098B - Selenized surface-modified ruthenium dioxide nanoparticle catalyst, and preparation method and application thereof - Google Patents
Selenized surface-modified ruthenium dioxide nanoparticle catalyst, and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 110
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
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- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000227 grinding Methods 0.000 claims abstract description 15
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- 239000000843 powder Substances 0.000 claims description 27
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- 239000004570 mortar (masonry) Substances 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 12
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- 230000000694 effects Effects 0.000 abstract description 19
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- 230000002829 reductive effect Effects 0.000 abstract description 9
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- 239000011669 selenium Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
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- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 84
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- 238000004519 manufacturing process Methods 0.000 description 19
- 238000006722 reduction reaction Methods 0.000 description 17
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- 239000001257 hydrogen Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 10
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- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
Abstract
The invention belongs to the technical field of new energy materials and electrochemical catalysis, and discloses a selenized surface-modified ruthenium dioxide nanoparticle catalyst, a preparation method and application thereof, wherein carbon black is used as a carrier, and ruthenium dioxide is fixed on the carrier by grinding; and modifying the selenium element on the surface of the ruthenium dioxide nano-particles through high-temperature calcination. According to the invention, the nano particles are processed, so that the specific surface area of the nano particles is effectively improved, the content of noble metals in the nano particles is relatively reduced, and the cost of the nano particles is reduced; the lithium sulfate has good stability, and the stability is not obviously reduced in a 0.1M lithium sulfate solution through a long-time current test for 24 hours; the selenized surface-modified ruthenium dioxide catalyst is a novel surface-modified material, has better NRR activity and has obvious advantages compared with the NRR activity of the existing noble metal/non-noble metal nitrogen reduction catalyst; is obviously better than the prior heteroatom-doped carbon material/noble metal catalyst.
Description
Technical Field
The invention belongs to the technical field of new energy materials and electrochemical catalysis, and particularly relates to a selenized surface-modified ruthenium dioxide nanoparticle catalyst, a preparation method and application.
Background
Ammonia (NH)3) As an important nitrogen-containing compound, the compound has wide application in the fields of agriculture, medicine, chemical industry and the like, and the hydrogen content in ammonia is 17.6 percent, so that the compound is an important energy storage intermediate and a carbon-free energy carrier. Currently, industrial large-scale synthesis of ammonia is mainly carried out by the Haber-Bosch process, which has two disadvantages: (1) needs to be carried out under high temperature and high pressure (300-500 ℃, 200-300atm), has large energy consumption,the annual average energy consumption accounts for 1-2% of the total energy consumption of the world; (2) high purity hydrogen is required as a raw material, and the hydrogen is generally converted from fossil fuel, and a large amount of CO is discharged2(about 1.5% of the annual emission of greenhouse gases). Therefore, the development of a clean synthetic ammonia technology with high efficiency and low energy consumption is urgently needed.
In recent years, the electro-catalytic synthesis of ammonia has attracted much attention by researchers, which can perform reactions at normal temperature and pressure, and which uses water and nitrogen as raw materials, and is considered as a potential synthetic ammonia technology to replace the industrial Haber-Bosch process. However, a great challenge faced by the current electrochemical ammonia synthesis technology is that the efficiency is too low (ammonia production rate and faraday current efficiency), mainly because the nitrogen-nitrogen triple bond in nitrogen is very firm at normal temperature and normal pressure, the nitrogen hydrogenation reaction is difficult to perform, the hydrogen evolution potential and the nitrogen reduction potential are very close, the water decomposition hydrogen production process which simultaneously occurs in the electrocatalytic nitrogen reduction ammonia production process becomes a competitive reaction, and the nitrogen reduction ammonia production efficiency (selectivity) is greatly reduced. Therefore, when an effective strategy is developed to inhibit the hydrogen production activity of the catalyst, the adsorption, activation and hydrogenation processes of nitrogen molecules on the surface of the catalyst are greatly promoted, and the method is extremely important for improving the efficiency of electro-catalytic nitrogen reduction for producing ammonia.
Ruthenium dioxide is a blue-black rutile crystal, is often applied to supercapacitors and electrochemical Oxygen Evolution Reaction (OER) and Hydrogen Evolution Reaction (HER), and shows excellent activity in hydrogen evolution reaction. Since the hydrogen evolution reaction competes with the Nitrogen Reduction Reaction (NRR), ruthenium dioxide has low activity in electrocatalytic nitrogen reduction. Furthermore, the high electrocatalytic activity is required to have a large specific surface area of the catalyst, and the current synthesis of ruthenium dioxide electrocatalysts with high specific surface area mainly depends on a complicated synthesis route. In addition, the stability of the ruthenium dioxide catalyst is poor due to the strong acid-erosiveness. Therefore, it remains challenging to explore a simple, low-cost manufacturing route to develop a highly efficient and stable ruthenium dioxide catalyst. In order to overcome the above disadvantages, researchers often use some carbon materials such as Graphene (GR) and Carbon Nanotube (CNT) as the substrate of the catalyst, which can improve the conductivity of the composite material on one hand and prevent LDH aggregation on the other hand, thereby improving its stability. Carbon-based catalyst materials have several advantages over metal catalysts, including their high abundance in earth crust, low cost, and tunability of structure and morphology. In addition, the catalytic activity of most metal catalysts depends on the intrinsic properties of the metal element, while the catalytically active sites of carbon groups can be modulated by the controlled introduction of dopants (e.g., "single"/"multiple" heteroatom doping), structural distortions/defects ("defect doping"), adsorbents ("charge transfer doping") or/and three-dimensional (3D) structures. This provides a powerful means for producing a series of highly efficient catalysts, making carbon-based essentially different from conventional metal-based catalysts, even with better versatility and greater optimization space.
The transition metal chalcogenide compound has unique chemical and electronic structures, and can effectively promote the electrocatalytic performance of the catalyst, so that the transition metal chalcogenide compound has attracted extensive academic attention in recent years. Various approaches have been developed to date to achieve optimum performance of such materials by introducing favorable interface and structural control. For example, exfoliation of bulk material into two-dimensional ultrathin nanosheets can greatly increase the number of active sites exposed; the crystal phase transformation, particularly the transformation of a stable cubic pyrite type into a metastable orthogonal phase pyrite type, can change the internal electronic structure of the stable cubic pyrite type, further influence the adsorption energy of reaction intermediate products, and finally lead to the favorable regulation and control of the catalytic performance. In addition, recent studies have found that the electrocatalytic performance of the material can be greatly improved by constructing a heterointerface of a metal chalcogenide and an oxide.
In summary, the problems of the prior art are as follows: the ammonia production rate and the Faraday current efficiency of the current catalyst used for electrochemically synthesizing ammonia are too low.
The difficulty of solving the technical problems is as follows:
(1) the traditional haber process for ammonia synthesis has been used for over one hundred years and requires high pressures of 20-50MPa and high temperatures of 500 ℃. Statistically, more than 1% of the worldwide energy is used in the process of ammonia synthesis each year. Meanwhile, the synthetic ammonia releases 400Mt of carbon dioxide every year in the world, which poses serious threat to the ecological environment. Therefore, a new approach for replacing the traditional Haber-Bosch method, such as the electrocatalytic nitrogen reduction synthesis of ammonia at normal temperature and pressure, with a green, safe and efficient method is attracting much attention.
(2) The electrochemical ammonia synthesis technology still faces significant challenges, and on one hand, the mass transfer process is severely limited by the low nitrogen solubility, and on the other hand, the selectivity and the activity are very low due to the strong hydrogen evolution competition reaction. The catalytic effect of the existing catalyst is mainly concentrated under high voltage, so that the design of the catalyst is very important for increasing nitrogen adsorption, inhibiting hydrogen evolution, accelerating reduction and realizing high ammonia yield under low voltage.
(3) Ruthenium dioxide is a good catalyst, is widely applied to electrocatalytic reaction, and shows excellent activity in hydrogen evolution reaction. Since the hydrogen evolution reaction competes with the Nitrogen Reduction Reaction (NRR), ruthenium dioxide has low activity in electrocatalytic nitrogen reduction.
The significance of solving the technical problems is as follows:
(1) the electrocatalytic nitrogen reduction at normal temperature used in the invention is green, efficient and environment-friendly, and can better meet the policy of green environmental protection, energy conservation and emission reduction proposed by the state.
(2) The carbon materials such as Graphene (GR) and carbon nano-tube (CNT) are used as the substrate of the catalyst, so that the conductivity of the composite material can be improved, and the aggregation of LDH is prevented, and the stability of the LDH is improved.
(3) The noble metal is processed into the nano particles, so that the number of exposed active sites can be greatly increased, the relative content of the noble metal in the catalyst can be reduced, and the production cost is reduced.
(4) The invention can effectively reduce the electric energy consumption by realizing high ammonia yield under low voltage, realize large ammonia yield by using less electric energy and realize high energy utilization.
(5) The surface selenylation modified ruthenium dioxide nanoparticle catalyst has high ammonia yield under-0.1V, opens up the application of ruthenium dioxide in the production of ammonia by nitrogen reduction, and provides a new idea for the design of other electrocatalytic nitrogen reduction catalysts.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a selenized surface-modified ruthenium dioxide nanoparticle catalyst, a preparation method and application thereof.
The invention is realized in such a way that a preparation method of a selenized surface-modified ruthenium dioxide nanoparticle catalyst comprises the following steps:
firstly, adding carbon and ruthenium trichloride into an agate mortar and grinding, respectively adding sodium hydroxide and sodium borohydride, and sequentially and respectively grinding; centrifuging the obtained powder in a centrifuge, and drying the sample for later use;
secondly, transferring the obtained ruthenium dioxide powder into a magnetic boat and paving the ruthenium dioxide powder, and scattering selenium powder into another magnetic boat; the magnetic boat was calcined and, after cooling to room temperature, the product was collected and ground to a powder in an agate mortar.
Further, in the first step, carbon and ruthenium trichloride are added into an agate mortar and fully ground, and sodium hydroxide and sodium borohydride are respectively added and fully ground in sequence.
Further, the powder obtained in the first step was centrifuged several times in a centrifuge until the pH of the solution became 7, and the sample was dried for use.
Further, the second step transfers the ruthenium dioxide powder to a magnetic boat and paves, and 2-15 times of selenium powder is scattered in another magnetic boat.
Further, in the second step, the magnetic boat is calcined for 0.5 to 6 hours at 250 ℃, 300 ℃ and 350 ℃ respectively.
Further, the heating rate of calcination is 2-10 ℃/min.
Different experimental conditions in the invention have different influences on experimental results, and can directly influence the experimental effect of the catalyst.
The invention also aims to provide the selenized surface-modified ruthenium dioxide nanoparticle catalyst prepared by the preparation method of the selenized surface-modified ruthenium dioxide nanoparticle catalyst.
The invention also aims to provide the application of the selenized surface modified ruthenium dioxide nanoparticle catalyst in electrocatalysis in a lithium sulfate solution.
The invention also aims to provide the application of the selenized surface modified ruthenium dioxide nanoparticle catalyst in electrocatalysis in a potassium hydroxide solution.
The invention also aims to provide the application of the selenized surface modified ruthenium dioxide nanoparticle catalyst in electrocatalysis in hydrochloric acid solution.
FIG. 5 is a graph of the catalyst obtained in example 2 in different electrolytes, provided by the example of the present invention;
in the figure: (a) a linear voltammogram; (b) a chronoamperometric curve; (c) corresponding ammonia production and faraday efficiency. The ammonia production amount of the catalyst in lithium sulfate reaches 54.05 mu gNH3h-1mg-1 cat.The Faraday efficiency reaches 26.1%. The ammonia yield in the hydrochloric acid reaches 42.85 mu gNH3h-1mg-1 cat.The Faraday efficiency was 2.3%. The ammonia yield in the potassium hydroxide reaches 7.8 mu gNH3h-1mg-1 cat.The Faraday efficiency was 0.05%.
In summary, the advantages and positive effects of the invention are: according to the invention, carbon black is taken as a carrier, metal ruthenium is fixed on the carrier through grinding, and then selenium is modified on the surface of ruthenium dioxide nanoparticles through high-temperature calcination. According to the selenized surface-modified ruthenium dioxide nanoparticle catalyst, the specific surface area is effectively improved by processing the selenized surface-modified ruthenium dioxide nanoparticle catalyst into nanoparticles (as shown in figures 2 and 3), the content of noble metals in the selenized surface-modified ruthenium dioxide nanoparticle catalyst is relatively reduced, and the cost of the selenized surface-modified ruthenium dioxide nanoparticle catalyst is further reduced. The used raw materials are easy to purchase and prepare; the lithium sulfate has good stability, and the stability is not obviously attenuated after a long-time current test for 24 hours in a 0.1M lithium sulfate solution; the ruthenium dioxide catalyst is a novel surface modification material, and as shown in figure 3, the ammonia production amount of the catalyst in lithium sulfate reaches 54.05 mu gNH3h-1mg-1 cat.The Faraday efficiency reaches 26.1%. The catalyst has good NRR activity, and has significant advantages compared with the NRR activity of the currently reported noble metal/non-noble metal nitrogen reduction catalyst; the NRR activity of the selenized surface-modified ruthenium dioxide nanoparticle catalyst, as shown in table 1, is significantly better than the heteroatom-doped carbon material/noble metal catalysts reported so far.
According to the invention, a precursor ruthenium dioxide is obtained by grinding, and then the ruthenium dioxide catalyst with selenized surface is prepared by calcining. Not only improves the conductivity, stability and specific surface area of the catalyst, but also obtains higher ammonia yield of the obtained nitrogen reduction catalyst, and the ammonia yield of the catalyst in lithium sulfate reaches 54.05 mu g as shown in figure 3NH3h-1mg-1 cat.The Faraday efficiency reaches 26.1%. The catalyst has better nitrogen reduction activity. The preparation method of the selenized surface-modified ruthenium dioxide nanoparticle catalyst is simple, is easy to operate and is convenient for large-scale production (as shown in figures 1 and 6).
Drawings
Fig. 1 is a flow chart of a preparation method of a selenized surface-modified ruthenium dioxide nanoparticle catalyst provided by an embodiment of the invention.
FIG. 2 is a transmission electron micrograph of the catalyst obtained in example 2 according to the present invention.
FIG. 3 is a transmission electron micrograph of the catalysts obtained in comparative example 1, example 1 and example 3 according to the present invention.
In the figure: (a) transmission electron micrograph of the catalyst obtained in comparative example 1; (b) transmission electron micrograph of catalyst obtained in example 1; (c) transmission electron micrograph of the catalyst obtained in example 3.
FIG. 4 shows RuO obtained in example 2 according to an embodiment of the present invention2-Se0.18NRR electrochemical property diagram of/C catalyst;
in the figure: (a) a linear voltammetry curve; (b) a chronoamperometric curve; (c) ultraviolet absorption spectroscopy; (d) corresponding ammonia production and faraday efficiency.
FIG. 5 is a graph of the NRR electrochemical properties of the catalysts obtained in comparative example 1, example 2 and example 3 provided in the examples of the present invention;
in the figure: (a) a chronoamperometric curve; (b) ultraviolet absorption spectroscopy; (c) the corresponding ammonia production; (d) the faraday efficiency.
FIG. 6 is a 24-hour chronoamperometric graph of the catalyst obtained in example 2 of the present invention in a lithium sulfate electrolyte.
FIG. 7 is a graph of the catalysts obtained in examples 1, 2 and 3 and comparative example 1 provided by the invention in different electrolytes;
in the figure: (a) a linear voltammogram; (b) a chronoamperometric curve; (c) corresponding ammonia production and faraday efficiency.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Aiming at the problems in the prior art, the invention provides a selenized surface-modified ruthenium dioxide nanoparticle catalyst, a preparation method and application thereof, and the invention is described in detail with reference to the accompanying drawings.
As shown in fig. 1, the preparation method of the selenized surface-modified ruthenium dioxide nanoparticle catalyst provided by the embodiment of the present invention includes the following steps:
s101: adding 30mg of carbon and ruthenium trichloride into an agate mortar, grinding together, respectively adding sodium hydroxide and sodium borohydride, and grinding respectively in sequence; the resulting powder was centrifuged several times in a centrifuge and the sample was dried for use.
S102: transferring 10mg of the obtained ruthenium dioxide powder into a magnetic boat, paving the ruthenium dioxide powder, and scattering 100mg of selenium powder into another magnetic boat; the magnetic boat was calcined at 250 ℃, 300 ℃ and 350 ℃ for 0.5-6h, respectively, at a heating rate of 2-10 ℃/min, and after cooling to room temperature, the resulting product was collected and ground into powder in an agate mortar for further use.
The invention provides a method for electrocatalysis application of a selenized surface modified ruthenium dioxide nanoparticle catalyst in lithium sulfate, potassium hydroxide and hydrochloric acid solution.
The technical solution of the present invention is further described with reference to the following specific examples.
Example 1:
the preparation method of the selenized surface modified ruthenium dioxide nanoparticle catalyst provided by the embodiment of the invention comprises the following steps:
in the first step, the precursor ruthenium dioxide was prepared by adding a quantity of carbon (30mg) and ruthenium trichloride in an agate mortar and grinding together. Then, sodium hydroxide and sodium borohydride were added, respectively, and ground in sequence. The resulting powder was centrifuged several times in a centrifuge until the pH of the solution was 7. The sample was then dried and ready for use.
Second step, RuO2-Se0.06Preparation of/C10 mg of the ruthenium dioxide powder obtained were transferred to a magnetic boat and laid flat. Then the selenium powder is scattered in another magnetic boat. Then calcining the magnetic boats at 250 ℃ respectively, wherein the heating rate is 2-10 ℃/min. After cooling to room temperature, the resulting product was collected and ground into a powder in an agate mortar for further use.
Example 2:
the preparation method of the selenized surface modified ruthenium dioxide nanoparticle catalyst provided by the embodiment of the invention comprises the following steps:
in the first step, the precursor ruthenium dioxide was prepared by adding a quantity of carbon (30mg) and ruthenium trichloride in an agate mortar and grinding together. Then, sodium hydroxide and sodium borohydride were added, respectively, and ground in sequence. The resulting powder was centrifuged several times in a centrifuge until the pH of the solution was 7. The sample was then dried and ready for use.
Second step, RuO2-Se0.18Preparation of/C10 mg of the ruthenium dioxide powder obtained were transferred to a magnetic boat and laid flat. Then the selenium powder is scattered in another magnetic boat. Then calcining the magnetic boats at 300 ℃ respectively, wherein the heating rate is 2-10 ℃/min. After cooling to room temperature, the resulting product was collected and ground into a powder in an agate mortar for further use.
Example 3:
the preparation method of the selenized surface modified ruthenium dioxide nanoparticle catalyst provided by the embodiment of the invention comprises the following steps:
in the first step, the precursor ruthenium dioxide was prepared by adding a quantity of carbon (30mg) and ruthenium trichloride in an agate mortar and grinding together. Then, sodium hydroxide and sodium borohydride were added, respectively, and ground in sequence. The resulting powder was centrifuged several times in a centrifuge until the pH of the solution was 7. The sample was then dried and ready for use.
Second step, RuO2-Se0.64Preparation of/C10 mg of the ruthenium dioxide powder obtained were transferred to a magnetic boat and laid flat. Then the selenium powder is scattered in another magnetic boat. Then calcining the magnetic boats at 350 ℃ respectively, wherein the heating rate is 2-10 ℃/min. After cooling to room temperature, the resulting product was collected and ground into a powder in an agate mortar for further use.
Comparative example 1:
the comparative example of the present invention provides a method for preparing a ruthenium dioxide nanoparticle catalyst, comprising the steps of:
an amount of carbon (30mg) and ruthenium trichloride were added to an agate mortar and ground together thoroughly. Then, sodium hydroxide and sodium borohydride were added, respectively, and ground in sequence. The resulting powder was centrifuged several times in a centrifuge until the pH of the solution was 7. The sample was then dried.
The invention prepares the selenized surface-modified ruthenium dioxide nanoparticle catalyst by a simple two-step method, optimizes the preparation process of ruthenium dioxide, and provides a thought for the preparation of the surface-modified nano material. The catalyst is modified by adding carbon base and selenium, so that the stability of ruthenium dioxide is improved, and the catalyst is processed into a nano-grade catalyst, so that the specific surface area of the catalyst is improved, and the catalyst has activity in NRR and high activity, and a high-activity NRR catalyst is designed.
It can be seen from FIG. 3 that the catalyst obtained in example 2 has good NRR activity and gives a good ammonia yield, which is superior to most of the catalysts currently available.
Further, comparing the different catalysts prepared by the method, it can be seen that the catalyst obtained in example 2 has the best NRR activity and excellent nitrogen reduction performance.
The catalyst obtained in example 2 was also tested in lithium sulfate, hydrochloric acid and potassium hydroxide electrolytes, respectively, and the NRR property of the catalyst in lithium sulfate solution was the best, although the performance in hydrochloric acid electrolyte was slightly poor, it also showed good stability and high NRR activity relative to other catalysts.
Fig. 2 is a TEM image of the catalyst prepared in example 2, and fig. 3 is a TEM image of the catalyst obtained in comparative example 1, and example 3 of the present invention. The ruthenium dioxide nano-particles successfully prepared by the method can be seen, the specific surface area of the ruthenium dioxide nano-particles is effectively increased, and the content of noble metal in the catalyst is reduced.
FIG. 4a is a linear voltammogram of the catalyst prepared in example 2 in a lithium sulfate solution saturated with nitrogen or argon. It can be seen that ammonia production begins below 0.1V. FIG. 4b is a chronoamperometric curve of the catalyst prepared in example 2; c is its ultraviolet absorption spectrum; d is the corresponding ammonia production and Faraday efficiency. As shown in the figure, the catalyst has high ammonia yield and Faraday efficiency in lithium sulfate solution at the voltage of-0.1V, and the ammonia yield and the Faraday efficiency can reach 54.05 mu g respectivelyNH3h-1mg-1 cat.And 26.1%.
FIG. 5 is a graph of electrochemical properties of catalysts prepared in examples 1, 2, 3 and comparative example 1, wherein a is a chronoamperometric curve; b is its ultraviolet absorption spectrum; c is the corresponding ammonia production; d is its corresponding faraday efficiency. As shown in the figure, the NRR performance of the catalyst after surface selenization modification is obviously improved, and the catalyst obtained in the example 2 has the best performance in a lithium sulfate solution under the voltage of-0.1V.
FIG. 6 is a chronoamperometric curve of example 2 in a lithium sulfate solution for 24 hours, showing that the catalyst prepared in example 2 has no significant decrease in stability after 24 hours of reaction, indicating good stability.
FIG. 7 shows the catalyst prepared in example 2NRR electrochemical properties in lithium sulfate, potassium hydroxide and hydrochloric acid solutions are tested, wherein a is a linear voltammetry curve, b is a chronoamperometry curve, and c is the corresponding ammonia production and Faraday efficiency. As shown in the figure, the NRR performance of the catalyst in the lithium sulfate solution is best, and the ammonia yield and the Faraday efficiency respectively reach 54.05 mu gNH3h-1mg-1 cat.And 26.1%. The performance of the ammonia-removing catalyst in hydrochloric acid is slightly poor, but the ammonia yield also reaches 42.71 mu gNH3h-1mg-1 cat.. Indicating that the catalyst has good NRR performance and can be applied to different solutions.
Table 1 shows the comparison of the catalyst prepared by the present invention with the recently reported results of NRR electrochemical catalysts at low overpotentials, indicating that the catalyst is significantly better than the heteroatom-doped carbon material/noble metal catalysts currently reported.
Table 1 comparison of the results of the catalysts prepared according to the invention with the recently reported NRR electrochemical catalysts at low overpotentials:
the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (5)
1. A preparation method of a selenized surface-modified ruthenium dioxide nanoparticle catalyst is characterized by comprising the following steps:
firstly, adding carbon and ruthenium trichloride into an agate mortar and grinding, respectively adding sodium hydroxide and sodium borohydride, and sequentially and respectively grinding; centrifuging the obtained powder in a centrifuge, and drying the sample for later use;
secondly, transferring the obtained ruthenium dioxide powder into a magnetic boat and paving the ruthenium dioxide powder, and scattering selenium powder into another magnetic boat; calcining the magnetic boat, cooling to room temperature, collecting the product, and grinding into powder in an agate mortar;
adding carbon and ruthenium trichloride into an agate mortar, grinding for 30 minutes, respectively adding sodium hydroxide and sodium borohydride, and respectively and fully grinding in sequence;
in the first step, the obtained powder is centrifuged in a centrifuge for several times, and a sample is dried for standby;
the second step is to transfer the ruthenium dioxide powder into a magnetic boat and lay the ruthenium dioxide powder flat, and then 2 to 15 times of selenium powder is scattered into another magnetic boat;
the second step is to calcine the magnetic boat for 0.5 to 10 hours at the temperature of 150-;
the heating rate of calcination is 2-10 ℃/min.
2. A selenized surface-modified ruthenium dioxide nanoparticle catalyst prepared by the preparation method of the selenized surface-modified ruthenium dioxide nanoparticle catalyst as claimed in claim 1.
3. The use of the selenized surface-modified ruthenium dioxide nanoparticle catalyst of claim 2 in electrocatalysis in lithium sulfate solution.
4. The use of the selenized surface-modified ruthenium dioxide nanoparticle catalyst of claim 2 in electrocatalysis in potassium hydroxide solution.
5. The use of the selenized surface-modified ruthenium dioxide nanoparticle catalyst of claim 2 in electrocatalysis in hydrochloric acid solution.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4427749A (en) * | 1981-02-02 | 1984-01-24 | Michael Graetzel | Product intended to be used as a photocatalyst, method for the preparation of such product and utilization of such product |
| CN101183718A (en) * | 2005-11-11 | 2008-05-21 | 三星Sdi株式会社 | Cathode catalyst for fuel cell, method of preparing same, and uses thereof |
| CN108707924A (en) * | 2018-05-16 | 2018-10-26 | 商丘师范学院 | Selenizing ruthenium nano particle modifies TiO2The Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array, preparation method and application |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4427749A (en) * | 1981-02-02 | 1984-01-24 | Michael Graetzel | Product intended to be used as a photocatalyst, method for the preparation of such product and utilization of such product |
| CN101183718A (en) * | 2005-11-11 | 2008-05-21 | 三星Sdi株式会社 | Cathode catalyst for fuel cell, method of preparing same, and uses thereof |
| CN108707924A (en) * | 2018-05-16 | 2018-10-26 | 商丘师范学院 | Selenizing ruthenium nano particle modifies TiO2The Electrocatalytic Activity for Hydrogen Evolution Reaction agent of nano-tube array, preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| Cyril Delacôte，et al."Aqueous-based synthesis of ruthenium–selenium catalyst for oxygen reduction reaction".《Faraday Discuss.》.2008, * |
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