CN111068738A - Preparation method and application of ruthenium-based hydrogen evolution electro-catalytic material - Google Patents
Preparation method and application of ruthenium-based hydrogen evolution electro-catalytic material Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 85
- 239000001257 hydrogen Substances 0.000 title claims abstract description 85
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 69
- 239000000463 material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 24
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 17
- 239000012153 distilled water Substances 0.000 claims abstract description 14
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000001338 self-assembly Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000000967 suction filtration Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000003792 electrolyte Substances 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 10
- 238000001354 calcination Methods 0.000 abstract description 8
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 abstract description 2
- 239000010453 quartz Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 9
- 229910000510 noble metal Inorganic materials 0.000 description 8
- 238000010586 diagram Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000010411 electrocatalyst Substances 0.000 description 5
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- 238000011056 performance test Methods 0.000 description 3
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- -1 transition metal sulfides Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
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- 150000004767 nitrides Chemical class 0.000 description 1
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- 238000006467 substitution reaction Methods 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
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/399—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
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- 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
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a preparation method and application of a ruthenium-based hydrogen evolution electro-catalysis material. The preparation method comprises the following steps: (1) mixing ruthenium trichloride, melamine and distilled water, and stirring for 0.5-2 h; mixing cyanuric acid with distilled water, and stirring for 0.5-1 h to obtain a cyanuric acid solution; wherein the molar ratio of the ruthenium trichloride to the melamine to the cyanuric acid is (0.005-0.2): 1: (0.5-1.5); (2) adding a melamine solution into a ruthenium trichloride and melamine solution, and stirring for 1-1.5 h to obtain a mixed solution; (3) carrying out suction filtration and drying on the mixed solution obtained in the step (2) to obtain a self-assembly precursor; (4) and (3) preserving the temperature for 3-5 h at 450-550 ℃ in the atmosphere of N2, and cooling to obtain the ruthenium-based hydrogen evolution electro-catalytic material. The invention can change the metal ruthenium into the monoatomic ruthenium when preparing the self-assembly precursor, highly disperse the ruthenium atom, and avoid the agglomeration of the metal ruthenium in the calcining process, thereby having excellent electrocatalytic hydrogen evolution effect.
Description
Technical Field
The invention relates to the technical field of electrocatalytic hydrogen evolution, in particular to a preparation method and application of a ruthenium-based hydrogen evolution electrocatalytic material.
Background
As a clean and environment-friendly energy source, the hydrogen has the characteristics of rich resources, high heat value, renewability and the like, is favored by numerous scholars, and is considered as a clean energy source capable of solving the problems of current energy shortage and environmental pollution. Among various hydrogen production processes, electrocatalytic water decomposition is an effective method for hydrogen production by a cathodic Hydrogen Evolution Reaction (HER), electric energy is converted into relatively stable chemical energy, other byproducts are not generated while hydrogen is obtained, and the method is environment-friendly and can realize sustainable hydrogen storage. In the process of electrocatalytic water decomposition and hydrogen evolution, overpotential of hydrogen evolution reaction is required to be reduced, and the rate of the electrocatalytic hydrogen evolution reaction is required to be improved, which can be realized by researching and developing a catalyst with excellent catalytic electrocatalytic hydrogen evolution reaction. Therefore, the research on the catalytic material has important significance on the electrocatalytic hydrogen production technology.
The catalysts for decomposing water and analyzing hydrogen by electrocatalysis mainly comprise non-noble metals and noble metals. Non-noble metal electrocatalysts are concentrated on transition metal sulfides, selenides, phosphides, carbides, nitrides and other semiconductor materials, but the catalytic activity of the non-noble metal electrocatalysts is low, so that the non-noble metal electrocatalysts cannot completely meet the industrial requirements temporarily. The noble metal electrocatalyst has more empty d orbitals in the original orbit, has smaller energy level spacing and is easy to coordinate with hydrogen atoms, so that the noble metal electrocatalyst has higher hydrogen evolution activity in electrocatalytic water decomposition. For example, a Pt-based catalytic material having an excellent electrocatalytic hydrogen evolution effect. However, the Pt-based catalytic material is expensive and has a small storage capacity, which limits its application to industrial hydrogen production.
Ruthenium (Ru) -based electrocatalytic materials have electrocatalytic hydrogen evolution effects comparable to commercial Pt/C, but their price is much lower than Pt, and thus have a great deal of development space. However, the ruthenium-based hydrogen evolution electrocatalytic material is easy to form agglomeration as a noble metal-based electrocatalytic material, so that the electrocatalytic effect of the ruthenium-based hydrogen evolution electrocatalytic material is weakened.
Therefore, how to disperse the ruthenium-based hydrogen evolution electro-catalytic material to improve the catalytic effect thereof is the research direction of the technicians in the field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to solve the problems that the existing ruthenium-based hydrogen evolution electro-catalysis material is easy to agglomerate, so that the electro-catalysis effect of the ruthenium-based hydrogen evolution electro-catalysis material is weakened and the catalysis effect is poor, and provides a preparation method of the ruthenium-based hydrogen evolution electro-catalysis material.
In order to solve the technical problem, the technical scheme adopted by the invention is as follows:
a preparation method of a ruthenium-based hydrogen evolution electro-catalytic material comprises the following steps:
(1) mixing ruthenium trichloride, melamine and distilled water, and stirring for 0.5-2 h; mixing cyanuric acid with distilled water, and stirring for 0.5-1 h to obtain a cyanuric acid solution; wherein the molar ratio of the ruthenium trichloride to the melamine to the cyanuric acid is (0.005-0.2): 1: (0.5-1.5);
(2) adding a melamine solution into a ruthenium trichloride and melamine solution, and stirring for 1-1.5 h to obtain a mixed solution;
(3) carrying out suction filtration and drying on the mixed solution obtained in the step (2) to obtain a self-assembly precursor;
(4) self-assembling precursors at N2Under the atmosphere of (450-.
Wherein, the suction filtration and drying in the step (3) are carried out for heat preservation at the temperature of 60-80 ℃ for 3-5 h after suction filtration.
Further, in the step (4), the heating is performed at a heating rate of (2-3) DEG C/min to (450-) 550 ℃.
The invention also provides application of the ruthenium-based hydrogen evolution electro-catalysis material in full-pH electrolyte, and the ruthenium-based hydrogen evolution electro-catalysis material is prepared by the method.
Compared with the prior art, the invention has the following beneficial effects:
1. the method uses simple raw materials to prepare the self-assembly structure, changes the metal ruthenium into the monoatomic ruthenium, has the characteristic of high dispersion, and avoids the agglomeration phenomenon of the metal ruthenium in the calcining process, so that the ruthenium atoms in the ruthenium-based hydrogen evolution electro-catalytic material obtained after calcining and cooling are dispersed, and the active sites of the ruthenium-based hydrogen evolution electro-catalytic material can be fully exposed; and the highly dispersed active sites of ruthenium are beneficial to the adsorption and reaction of hydrogen atoms, and can realize excellent electrocatalytic hydrogen evolution effect.
2. The raw materials for preparing the self-assembly precursor are low in price and rich in source; and the method for preparing the self-assembly precursor is simple and feasible, and the conditions are controllable.
3. The ruthenium-based hydrogen evolution electro-catalysis material prepared by the invention is suitable for full-pH electrolyte and has important application prospect.
Drawings
FIG. 1 is a TEM dark field and MAPPING image of the self-assembled precursor prepared in example 1, wherein a is the atomic distribution diagram of Ru, b is the atomic distribution diagram of O, C is the atomic distribution diagram of C, d is the atomic distribution diagram of Cl, and e is the atomic distribution diagram of N.
Fig. 2 is an XRD diffractogram of the ruthenium-based hydrogen evolution electrocatalytic material prepared in example 1.
FIG. 3 is a TEM + HRTEM + MAPPING graph of the ruthenium-based hydrogen evolution electrocatalytic material prepared in example 1.
FIG. 4 shows that the ruthenium-based hydrogen evolution electrocatalytic material prepared in example 1 is at 0.5M H2LSV map in SO 4.
FIG. 5 shows that the ruthenium-based hydrogen evolution electrocatalytic material prepared in example 1 is at 0.5M H2Stability performance test pattern in SO 4.
FIG. 6 is a graph of LSV in 1M KOH for the ruthenium-based hydrogen evolution electrocatalytic material prepared in example 1.
FIG. 7 shows that the ruthenium-based hydrogen evolution electrocatalytic material prepared in example 2 is at 0.5M H2LSV map in SO 4.
FIG. 8 shows that the ruthenium-based hydrogen evolution electrocatalytic material prepared in example 3 is at 0.5M H2LSV map in SO 4.
FIG. 9 shows that the ruthenium-based hydrogen evolution electrocatalytic material prepared in example 4 is at 0.5M H2LSV map in SO 4.
Detailed description of the preferred embodiments
The invention will be further explained with reference to the drawings and the embodiments.
Preparation of ruthenium-based hydrogen evolution electro-catalytic material
Example 1
(1) In a 100mL beaker A, a stirrer was placed, then 0.2g of melamine, and 10mg of ruthenium trichloride were added, and after 40mL of distilled water was added, beaker A was placed on a magnetic stirrer and stirred for 1 hour. In a 50mL beaker B, 0.2g of cyanuric acid was added, followed by 40mL of distilled water, and dissolved by sonication for 30 minutes.
(2) And pouring the dissolved melamine solution, namely the beaker B, into the melamine solution, namely the beaker A, in which the ruthenium trichloride is dissolved, and continuously stirring for 1 hour at room temperature to obtain a mixed solution.
(3) Then, the mixed solution in the beaker A was filtered with suction and dried under the drying condition of 80 ℃ for 4 hours to obtain a self-assembled precursor, as shown in FIG. 1. As can be seen from a in fig. 1, the prepared self-assembled precursor has a high dispersion of ruthenium atoms. Therefore, the agglomeration of ruthenium atoms in the calcining process can be avoided, and the dispersion of the ruthenium atoms in the prepared ruthenium-based hydrogen evolution electro-catalytic material is ensured. It can be seen from b, c, d, e in fig. 1 that the other elements in the self-assembled precursor are also highly dispersed, and thus the elements of the obtained self-assembled precursor are uniformly dispersed.
(4) The self-assembled precursor was transferred to a quartz boat, covered with a lid and placed in a tube furnace for calcination. After the quartz boat is put into the tube furnace, the instrument is installed, and after the ventilating device, the tail gas treatment device and the exhaust device are checked to work normally, N is introduced2For 20 minutes to evacuate the air in the tube. The heating rate is 2.3 ℃/min, the maximum temperature is 550 ℃, the holding time is 4 hours, and then a heating switch is started to start heating. And taking out the quartz boat after the tubular furnace is cooled to room temperature to obtain the ruthenium-based hydrogen evolution electro-catalytic material. FIG. 2 is an XRD diffraction pattern of the prepared ruthenium-based hydrogen evolution electro-catalytic material, and it can be seen that the prepared ruthenium-based hydrogen evolution electro-catalytic material conforms to all XRD peaks of ruthenium, so that the main component of the ruthenium is ruthenium. FIG. 3 is a HRTEM image of the prepared ruthenium-based hydrogen evolution electrocatalytic material, and the result also coincides with XRD thereof. FIG. 4 is a Map of the prepared ruthenium-based hydrogen evolution electrocatalytic materialping picture proves that the ruthenium element in the prepared ruthenium-based hydrogen evolution electro-catalysis material is highly dispersed.
Example 2:
(1) in a 100mL beaker A, a stirrer was placed, then 0.2g of melamine, and 1mg of ruthenium trichloride were added, and after 40mL of distilled water was added, beaker A was placed on a magnetic stirrer and stirred for 1 hour. In a 50mL beaker B, 0.2g of cyanuric acid was added, followed by 40mL of distilled water, and dissolved by sonication for 30 minutes.
(2) A molten melamine solution, beaker B, was poured into a melamine solution, beaker a, containing ruthenium trichloride, and the mixture was stirred at room temperature for 1 hour to obtain a mixed solution.
(3) And then, carrying out suction filtration on the mixed solution in the beaker A, and drying the mixed solution at the drying condition of 80 ℃ for 4 hours to obtain the self-assembly precursor.
(4) The self-assembled precursor was transferred to a quartz boat, covered with a lid and placed in a tube furnace for calcination. After the quartz boat is put into the tube furnace, the instrument is installed, and after the ventilating device, the tail gas treatment device and the exhaust device are checked to work normally, N is introduced2For 20 minutes to evacuate the air in the tube. Heating at a rate of 2.3 ℃/min, at a maximum temperature of 550 ℃, keeping for 4 hours, and then starting a heating switch to start heating; and taking out the quartz boat after the tubular furnace is cooled to room temperature to obtain the ruthenium-based hydrogen evolution electro-catalytic material.
Example 3:
(1) in a 100mL beaker A, a stirrer was placed, then 0.2g of melamine, and 20mg of ruthenium trichloride were added, and after 40mL of distilled water was added, beaker A was placed on a magnetic stirrer and stirred for 1 hour. In a 50mL beaker B, 0.2g of cyanuric acid was added, followed by 40mL of distilled water, and dissolved by sonication for 30 minutes.
(2) A molten melamine solution, beaker B, was poured into a melamine solution, beaker a, containing ruthenium trichloride, and the mixture was stirred at room temperature for 1 hour to obtain a mixed solution.
(3) And then, carrying out suction filtration on the mixed solution in the beaker A, and drying the mixed solution at the drying condition of 80 ℃ for 4 hours to obtain the self-assembly precursor.
(4) The self-assembled precursor was transferred to a quartz boat, covered with a lid and placed in a tube furnace for calcination. After the quartz boat is put into the tube furnace, the instrument is installed, and after the ventilating device, the tail gas treatment device and the exhaust device are checked to work normally, N is introduced2For 20 minutes to evacuate the air in the tube. Heating at a rate of 2.3 ℃/min, at a maximum temperature of 550 ℃, keeping for 4 hours, and then starting a heating switch to start heating; and taking out the quartz boat after the tubular furnace is cooled to room temperature to obtain the ruthenium-based hydrogen evolution electro-catalytic material.
Example 4:
(1) in a 100mL beaker A, a stirrer was placed, then 0.2g of melamine, and 40mg of ruthenium trichloride were added, and after 40mL of distilled water was added, beaker A was placed on a magnetic stirrer and stirred for 1 hour. In a 50mL beaker B, 0.2g of cyanuric acid was added, followed by 40mL of distilled water, and dissolved by sonication for 30 minutes.
(2) A molten melamine solution, beaker B, was poured into a melamine solution, beaker a, containing ruthenium trichloride, and the mixture was stirred at room temperature for 1 hour to obtain a mixed solution.
(3) And then, carrying out suction filtration on the mixed solution in the beaker A, and drying the mixed solution at the drying condition of 80 ℃ for 4 hours to obtain the self-assembly precursor.
(4) The self-assembled precursor was transferred to a quartz boat, covered with a lid and placed in a tube furnace for calcination. After the quartz boat is put into the tube furnace, the instrument is installed, and after the ventilating device, the tail gas treatment device and the exhaust device are checked to work normally, N is introduced2For 20 minutes to evacuate the air in the tube. Heating at a rate of 2.3 ℃/min, at a maximum temperature of 550 ℃, keeping for 4 hours, and then starting a heating switch to start heating; and taking out the quartz boat after the tubular furnace is cooled to room temperature to obtain the ruthenium-based hydrogen evolution electro-catalytic material.
Hydrogen evolution performance test of ruthenium-based hydrogen evolution electrocatalytic material
The ruthenium-based hydrogen evolution electro-catalytic material prepared in the embodiment 1-4 is used for electro-catalytic hydrogen evolution, and the specific steps are as follows:
1) preparation of test electrodes: weighing 1mg of ruthenium-based hydrogen evolution electro-catalysis material, adding the ruthenium-based hydrogen evolution electro-catalysis material into 190ul of ethanol/water solution (volume ratio is 1: 1), adding 10ul of Nafion solution, and then carrying out ultrasonic treatment for 30 minutes to ensure that the catalysis material is uniformly dispersed; 4ul of the mixed solution after ultrasonic treatment is dripped on a glassy carbon electrode, and the mixed solution is naturally dried for later use.
2) Electrocatalytic hydrogen evolution test: a three-electrode test mode is selected, a reference electrode is a saturated calomel electrode, a counter electrode is a carbon rod electrode, and a working electrode is a glassy carbon electrode loaded with a catalytic material. Wherein the acid electrolyte is 0.5M H2SO4The alkaline electrolyte is 1M KOH.
The hydrogen evolution performance of a commercial 20 wt% Pt/C hydrogen evolution electrocatalytic material was tested as described above using a commercial 20 wt% Pt/C hydrogen evolution electrocatalytic material as a control. The results are shown in FIGS. 4 to 9. Wherein, FIG. 4 shows that the ruthenium-based hydrogen evolution electrocatalytic material prepared in example 1 is at 0.5M H2SO4As shown in the graph of the middle stability performance test, as can be seen from FIG. 4, the ruthenium-based hydrogen evolution electrocatalytic material prepared in example 1 has good long-term stability in an acid electrolyte, and when the current density reaches-10 mA cm after 1000 cycles-2The reason why the required overpotential is slightly reduced from before 1000 cycles is that the whole circuit is unstable before 1000 cycles and the circuit condition is stable after 1000 cycles, and the prepared electrocatalytic material has excellent durability and stability, thus showing excellent electrocatalytic hydrogen evolution effect. Fig. 5 and 6 are graphs showing the electrolytic performance of the ruthenium-based hydrogen evolution electrocatalytic material prepared in example 1 in an acidic or alkaline electrolyte. FIG. 8 shows that the ruthenium-based hydrogen evolution electrocatalytic material prepared in example 3 is at 0.5M H2SO4LSV map of (1). FIG. 9 shows that the ruthenium-based hydrogen evolution electrocatalytic material prepared in example 4 is at 0.5M H2SO4LSV map of (1). As can be seen from FIGS. 5, 6, 8 and 9, the hydrogen evolution effect of the ruthenium-based hydrogen evolution electrocatalytic material is more excellent than that of commercial 20 wt% Pt/C, and reaches-10 mA cm-2The current density of (A) requires only an overpotential of (18-26) mV, whereas 20 wt% Pt/C requires an overpotential of-53 mV, indicating that as the ruthenium content increases, the catalytic performance of the ruthenium-based hydrogen evolution electrocatalytic material increases, since more ruthenium atoms are dispersed in the catalytic material, providingMore active sites are provided, so that the hydrogen evolution can be catalyzed more effectively. FIG. 7 shows that the ruthenium-based hydrogen evolution electrocatalytic material prepared in example 2 is at 0.5M H2SO4The LSV diagram in (1) shows that the ruthenium-based hydrogen evolution electrocatalytic material prepared in example 2 is 0.5M H2SO4The medium potential is lower than that of a commercial 20 wt% Pt/C hydrogen evolution electrocatalytic material, and the low overpotential can meet the requirement of hydrogen evolution, so that more hydrogen energy can be created by using less electric energy.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the technical solutions, and those skilled in the art should understand that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all that should be covered by the claims of the present invention.
Claims (4)
1. A preparation method of a ruthenium-based hydrogen evolution electro-catalytic material is characterized by comprising the following steps:
(1) mixing ruthenium trichloride, melamine and distilled water, and stirring for 0.5-2 h; mixing cyanuric acid with distilled water, and stirring for 0.5-1 h to obtain a cyanuric acid solution; wherein the molar ratio of the ruthenium trichloride to the melamine to the cyanuric acid is (0.005-0.2): 1: (0.5-1.5);
(2) adding a melamine solution into a ruthenium trichloride and melamine solution, and stirring for 1-1.5 h to obtain a mixed solution;
(3) carrying out suction filtration and drying on the mixed solution obtained in the step (2) to obtain a self-assembly precursor;
(4) self-assembling precursors at N2Under the atmosphere of (450-.
2. The method for preparing a ruthenium-based hydrogen evolution electrocatalytic material as set forth in claim 1, wherein the drying by suction filtration in the step (3) is performed after suction filtration and then the temperature is maintained at (60-80) ℃ for (3-5) h.
3. The method for preparing a ruthenium-based hydrogen evolution electrocatalytic material as set forth in claim 1, wherein the step (4) is performed by heating to (450-.
4. Use of a ruthenium-based hydrogen evolution electrocatalytic material in a full pH electrolyte, wherein the ruthenium-based hydrogen evolution electrocatalytic material is prepared by the method of any one of claims 1 to 3.
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