CN117512641A - Carbon-supported ruthenium-gallium intermetallic compound, preparation method and application thereof - Google Patents
Carbon-supported ruthenium-gallium intermetallic compound, preparation method and application thereof Download PDFInfo
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- CN117512641A CN117512641A CN202311693207.7A CN202311693207A CN117512641A CN 117512641 A CN117512641 A CN 117512641A CN 202311693207 A CN202311693207 A CN 202311693207A CN 117512641 A CN117512641 A CN 117512641A
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- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 35
- 229910000765 intermetallic Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 19
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 6
- 150000002258 gallium Chemical class 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 150000003303 ruthenium Chemical class 0.000 claims abstract description 5
- 238000001704 evaporation Methods 0.000 claims abstract description 4
- 230000009467 reduction Effects 0.000 claims description 36
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 8
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 7
- 239000003011 anion exchange membrane Substances 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 229940044658 gallium nitrate Drugs 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- ZVYYAYJIGYODSD-LNTINUHCSA-K (z)-4-bis[[(z)-4-oxopent-2-en-2-yl]oxy]gallanyloxypent-3-en-2-one Chemical compound [Ga+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O ZVYYAYJIGYODSD-LNTINUHCSA-K 0.000 claims description 2
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- FYWVTSQYJIPZLW-UHFFFAOYSA-K diacetyloxygallanyl acetate Chemical compound [Ga+3].CC([O-])=O.CC([O-])=O.CC([O-])=O FYWVTSQYJIPZLW-UHFFFAOYSA-K 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000002070 nanowire Substances 0.000 claims description 2
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 2
- 239000007809 chemical reaction catalyst Substances 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 28
- 230000000694 effects Effects 0.000 abstract description 18
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- 230000007423 decrease Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 10
- 238000009210 therapy by ultrasound Methods 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 229920000557 Nafion® Polymers 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
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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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
-
- 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
-
- 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
- C25B11/093—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 at least one noble metal or noble metal oxide and at least one non-noble metal oxide
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of catalysts, and particularly relates to a preparation method and application of a carbon-supported ruthenium-gallium intermetallic compound, wherein the preparation method comprises the following steps: (1) Dispersing ruthenium salt, gallium salt and a carbon carrier in a solvent, ultrasonically stirring, heating, evaporating the solvent, further drying the obtained sample, and grinding to obtain precursor solid powder; (2) And reducing the precursor solid powder in a reducing atmosphere to obtain the carbon-supported ruthenium-gallium intermetallic compound. According to the invention, by introducing low-melting-point and relatively-low-cost metallic gallium, the temperature in the catalyst synthesis process can be reduced, the energy consumption can be reduced, the cost of the ruthenium-based catalyst can be reduced, the electrocatalytic activity can be improved, and the problems of poor activity and over-high cost in the alkaline HOR, HER, OER can be effectively solved.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a carbon-supported ruthenium-gallium intermetallic compound, a preparation method and application thereof.
Background
Energy conservation and environmental protection are two most urgent tasks on the road of the sustainable development of the 21 st century. With the rapid growth of energy demand, the increase of environmental pollution, and the increase of carbon dioxide concentration in the atmosphere caused by the overuse of fossil fuels. Intensive research activities are being conducted to better utilize renewable energy sources that are environmentally friendly. Hydrogen, which is an energy carrier with zero carbon content, has the highest energy density among the existing fuels, has a mass heating value 4.8 times that of coal, and is considered to be the most promising clean and renewable energy source. Electrolysis of water and fuel cells are key technologies for achieving hydrogen economy. Currently, proton Exchange Membrane Fuel Cells (PEMFCs) and proton exchange membrane water electrolytic cells (pemffs) in acidic media need to operate in a strongly acidic and highly oxidative working environment, so that the devices are more dependent on expensive noble metal materials such as iridium, platinum, etc., resulting in excessive cost and greatly limiting their wide application. In contrast, anion Exchange Membrane Fuel Cells (AEMFCs) and anion exchange membrane water electrolysis cells (AEMWEs) in lower cost alkaline media have a greater potential for commercial application.
However, in alkaline media, the reaction kinetics of the anodic oxidation reaction (Hydrogen oxidation reaction, HOR) of AEMFCs, the cathodic hydrogen evolution reaction (Hydrogen evolution reaction, HER) of AEMWEs, and the anodic oxygen evolution reaction (Oxygen evolution reaction, OER) are slow. In addition, currently, a catalyst capable of being simultaneously applied to the alkalinity HOR, HER, OER is rarely reported, and the multifunctional catalyst can greatly reduce the assembly cost and the operation condition of hydrogen circulation equipment, and has important significance for the development of hydrogen energy economy. Therefore, the development of a multifunctional catalyst with low cost, high activity and simultaneous application to the alkalinity HOR, HER, OER has important significance for promoting the large-scale popularization and application of AEMFCs and PEMFCs.
Currently, basic HOR, HER, OER catalysts are mainly noble metal-based catalysts, although some reports indicate that non-noble metal-based electrocatalysts also exhibit some HOR, HER, OER catalytic activity, there is still a great gap from the catalytic activity of noble metal-based catalysts. Ruthenium is relatively low in price in noble metals, the reserve is more abundant, and the price is only 20% of that of platinum. Meanwhile, ruthenium has a platinum-like hydrogen binding capacity and a suitable oxygen intermediate binding capacity, which exhibits good HOR/HER/OER catalytic activity, but has room for improvement in catalytic activity compared to the commercial benchmarks for each reaction. Therefore, development of a multifunctional ruthenium-based catalyst having high activity is urgently required.
Disclosure of Invention
According to the requirements, the invention aims to provide a carbon-supported ruthenium-gallium intermetallic compound, a preparation method and application thereof in electrocatalytic alkaline HOR/HER/OER reaction, and aims to develop a multifunctional ruthenium-based catalyst and improve the catalytic activity thereof, so that large-scale popularization and application of AEMFCs and AEMWEs are promoted.
To achieve the above object, according to a first aspect of the present invention, there is provided a method for preparing a ruthenium-gallium-on-carbon intermetallic compound, comprising:
(1) Dispersing ruthenium salt, gallium salt and a carbon carrier in a solvent, ultrasonically stirring, heating and evaporating the solvent, further drying the obtained solid product, and grinding to obtain precursor solid powder;
(2) And reducing the precursor solid powder in a reducing atmosphere to obtain the carbon-supported ruthenium-gallium intermetallic compound.
Preferably, the temperature rising rate of the reduction step is 5-10 ℃/min, the reduction temperature is 600-800 ℃, and the reduction time is 2-10 h.
Preferably, the mass fraction of ruthenium element in the precursor solid powder of the step (1) is 15% -20%.
Preferably, the atomic ratio of ruthenium to gallium in the precursor solid powder of step (1) is 1: (0.5-1).
Preferably, the ruthenium salt is at least one of ruthenium chloride, ruthenium acetylacetonate and ruthenium acetate; the gallium salt is at least one of gallium nitrate, gallium acetate and gallium acetylacetonate.
Preferably, the carbon carrier is at least one of carbon black, graphene, carbon nanotubes and carbon nanowires.
Preferably, the reducing atmosphere in the step (2) is argon-hydrogen mixed gas, wherein the hydrogen volume ratio is 5% -10%.
Preferably, the solvent in the step (1) is at least one of water and ethanol, the ultrasonic stirring time is 0.5-2 h, and the heating temperature is 55-70 ℃.
According to another aspect of the present invention, there is also provided a carbon-supported ruthenium-gallium intermetallic compound prepared by the above method, which is a pure-phase ruthenium-gallium intermetallic compound.
According to a further aspect of the present invention there is provided the use of a carbon supported ruthenium gallium intermetallic compound as described above as a cathode HER and anode OER catalyst for a basic anion exchange membrane fuel cell anode HOR catalyst or a basic anion exchange membrane water electrolysis cell.
In general, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
(1) According to the invention, low-melting-point and low-cost metallic gallium is introduced into the ruthenium-based catalyst, so that the temperature in the catalyst synthesis process can be reduced, the energy consumption can be reduced, the cost of the ruthenium-based catalyst can be reduced, the electrocatalytic activity can be improved, and the problems of poor activity and overhigh cost in alkaline HOR, HER, OER can be effectively solved.
(2) The preparation method adopted by the invention has the unique advantages of low energy consumption, simplicity, high efficiency, mildness, low cost, strong repeatability and the like, and has the potential of large-scale preparation.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of ruthenium-gallium intermetallic compounds loaded on carbon at a reduction temperature of 600℃at 700℃and 800℃in example 1.
FIG. 2 is an X-ray diffraction (XRD) pattern of ruthenium-gallium intermetallic compounds loaded on carbon at a reduction temperature of 600℃at 700℃and 800℃in example 2.
FIG. 3 is an X-ray photoelectron spectroscopy (XPS) spectrum of a carbon-supported ruthenium gallium intermetallic compound at a reduction temperature of 600℃in example 1.
FIG. 4 is a graph showing the polarization of HOR-LSV of ruthenium-gallium intermetallic compounds loaded on carbon at 600℃at 700℃and 800℃in example 1, with an electrolyte solution of 0.1M KOH solution;
FIG. 5 is a graph showing the polarization of HER-LSV of ruthenium-gallium intermetallic compounds loaded on carbon at 600, 700, 800℃reduction temperature in example 1, with electrolyte solution of 1M KOH solution;
FIG. 6 is an OER-LSV polarization curve of ruthenium-gallium intermetallic compounds loaded on carbon at 600 ℃, 700 ℃, 800 ℃ reduction temperature in example 1, electrolyte solution 1M KOH solution.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Example 1
The embodiment provides a carbon-supported ruthenium-gallium intermetallic compound, which is prepared by the following steps:
40mg of Vulcan carbon is uniformly dispersed in 5ml of ruthenium chloride and gallium nitrate aqueous solution, and the mixture is subjected to ultrasonic treatment and stirring for 30min. Stirring the obtained mixed solution at 65 ℃, carrying out ultrasonic treatment until the water solvent is evaporated to dryness to obtain a solid product, grinding the solid product in an agate mortar to obtain precursor solid powder (wherein the loading amount of ruthenium is 15 percent, the atomic ratio of ruthenium to gallium is 1:1), and carrying out Ar/H on the obtained precursor solid powder at a volume ratio of 10 percent 2 The mixed atmosphere is reduced, the heating rate is 5 ℃/min, the temperature gradient of the reduction is 600 ℃, 700 ℃ and 800 ℃, and the reduction time is 2 hours.
Example 2
33.1g of Vulcan carbon was uniformly dispersed in 5ml of an aqueous solution of ruthenium chloride and gallium nitrate, and stirred for 30 minutes with ultrasound. Stirring the obtained mixed solution at 65 ℃, carrying out ultrasonic treatment until the water solvent is evaporated to dryness to obtain a solid product, grinding the solid product in an agate mortar to obtain precursor solid powder (wherein the loading amount of ruthenium is 20 percent, the atomic ratio of ruthenium to gallium is 1:1), and carrying out Ar/H on the obtained precursor solid powder at a volume ratio of 5 percent 2 Reducing in mixed atmosphere at heating rate of 5 deg.c/min and furtherThe original temperature gradient is 600 ℃, 700 ℃ and 800 ℃ respectively, and the reduction time is 2 hours.
Comparative example 1
The comparative example provides a carbon-supported ruthenium simple substance as a comparative sample, and the preparation method is as follows:
the Vulcan carbon is evenly dispersed in 5ml of ruthenium chloride aqueous solution, and the solution is stirred for 30min by ultrasonic treatment. The thus obtained mixed solution was stirred at 65℃and sonicated until the water solvent was evaporated to dryness to obtain a precursor solid powder (wherein the loading of ruthenium was 20%), and the obtained precursor solid powder was subjected to 10% Ar/H 2 The mixed atmosphere is reduced, the heating rate is 5 ℃/min, the reduction temperature is 150 ℃, and the reduction time is 2h.
Comparative example 2
The comparative example provides a carbon-supported platinum simple substance as a comparative sample, and the preparation method is as follows:
the Vulcan carbon is evenly dispersed in 5ml of ruthenium chloride aqueous solution, and the solution is stirred for 30min by ultrasonic treatment. Stirring the obtained mixed solution at 65 ℃, carrying out ultrasonic treatment until the water solvent is evaporated to dryness to obtain precursor solid powder (wherein the loading amount of Ru is 20%), and carrying out 10% Ar/H on the obtained precursor solid powder 2 The mixed atmosphere is reduced, the heating rate is 5 ℃/min, the reduction temperature is 150 ℃, and the reduction time is 2h.
Comparative example 3
The comparative example provides a ruthenium dioxide as a control, which is prepared as follows:
the Vulcan carbon is evenly dispersed in 5ml of ruthenium chloride aqueous solution, and the solution is stirred for 30min by ultrasonic treatment. Stirring the obtained mixed solution at 65deg.C, and evaporating to dryness with ultrasonic wave to obtain precursor solid powder (with ruthenium load of 20%) at O 2 Oxidizing in atmosphere at a heating rate of 5 ℃/min, an oxidizing temperature of 400 ℃ and an oxidizing time of 2h.
Application testing
The carbon-supported ruthenium gallium intermetallic compound of example 1 was subjected to alkali HOR, HER and OER tests with the carbon-supported ruthenium simple substance, carbon-supported platinum simple substance, ruthenium dioxide prepared in comparative example 1, comparative example 2, comparative example 3.
For the alkaline HOR test, 1mg of catalyst powder and 3mg of Vulcan carbon powder were added to 1mL of an isopropyl alcohol/Nafion mixed solution to formulate an ink (0.1 wt% Nafion). And (5) carrying out ultrasonic treatment on the ink for 15min, and uniformly mixing. And measuring 5 mu L of ink by using a microsyringe, dripping a small amount of ink on the surface of the glassy carbon electrode for many times, and naturally drying in air. The carbon rod is used as a working electrode, the carbon rod is used as an auxiliary electrode, and the reversible hydrogen electrode is used as a reference electrode. The electrolyte solution was a freshly prepared 0.1M KOH electrolyte. Charging 30min H into 0.1M KOH electrolyte 2 Saturated, set at 1600rpm, and scan at a scan speed of 0.005-V s in a voltage range of-0.05-0.15V -1 Scanning to obtain LSV curve.
For alkaline HER testing, 5mg of catalyst powder was added to 1mL of isopropyl alcohol/Nafion mixed solution to formulate an ink (0.1 wt% Nafion). And (5) carrying out ultrasonic treatment on the ink for 15min, and uniformly mixing. And measuring 10 mu L of ink by using a microsyringe, dripping a small amount of ink on the surface of the glassy carbon electrode for many times, and naturally drying in air. The carbon rod is used as a working electrode, the carbon rod is used as an auxiliary electrode, and the reversible hydrogen electrode is used as a reference electrode. The electrolyte solution is a newly prepared 1M KOH electrolyte. Charging 30min H into 1M KOH electrolyte 2 Saturated, set at 1600rpm, and scan at a scan speed of 0.005-V s in a voltage range of-0.3-0.05V -1 Scanning to obtain LSV curve.
For alkaline OER testing, 5mg of catalyst powder was added to 1mL of an isopropyl alcohol/Nafion mixed solution to formulate an ink (0.1 wt% Nafion). And (5) carrying out ultrasonic treatment on the ink for 15min, and uniformly mixing. And measuring 10 mu L of ink by using a microsyringe, dripping a small amount of ink on the surface of the glassy carbon electrode for many times, and naturally drying in air. The carbon rod is used as a working electrode, the carbon rod is used as an auxiliary electrode, and the reversible hydrogen electrode is used as a reference electrode. The electrolyte solution is a newly prepared 1M KOH electrolyte. Introducing 30min N into 1M KOH electrolyte 2 Saturated, activated for 100 circles within the range of 0.05-1.2V, and the scanning speed is 0.2V s-1. Changing new 1M KOH electrolyte, setting the rotating speed to 1600rpm, and setting the scanning speed to 0.005-V s in the voltage range of 1.2-1.7V -1 Scanning to obtain LSV curve.
FIG. 1 shows XRD patterns of ruthenium-gallium intermetallic compounds (RuGa/C) carried on carbon at different reduction temperatures in example 1, and a broad peak of the material at about 26℃is attributed to a diffraction peak of the (002) face of the carbon support. At the same time, other characteristic peaks can be well indexed to the body centered cubic RuGa (PDF No. 96-152-3921), where Ga atoms occupy 8 vertices of a cell, while Ru atoms are located in the center of the body, confirming successful synthesis of RuGa/C. It can be seen that the particle size and crystallinity of RuGa increases as the reduction temperature increases.
Figure 2 XRD patterns of carbon-supported ruthenium gallium intermetallic compounds (RuGa/C) at different reduction temperatures in example 2, as shown in the figure, changing the loading of Ru and the volume ratio of hydrogen at the time of reduction, can also obtain RuGa intermetallic compounds having a body-centered cubic structure. As the reduction temperature increases, the particle size and crystallinity of RuGa increases, consistent with the conclusion of example 1.
FIG. 3 is an X-ray photoelectron Spectrometry (XPS) spectrum of RuGa/C at 600℃reduction temperature in example 1, from which it can be seen that there are four elements Ru, ga, C, O in the sample, O being present due to uncontrolled oxidation of the sample by exposure to air.
FIG. 4 shows the polarization curves of RuGa/C at different reduction temperatures in example 1 and HOR-LSV of the carbon-supported ruthenium simple substance (Ru/C) and the carbon-supported platinum simple substance (Pt/C) in comparative example 1 and comparative example 2, showing that the activity of the catalyst is in a decreasing trend with the increase of the reduction temperature, and the activity of the material reaches the peak when the reduction temperature is 600 ℃, and is superior to Ru/C and Pt/C, which shows that the introduction of gallium element improves the catalytic activity of the material. The activity of the catalyst tends to decrease with increasing reduction temperature, because an increase in particle size caused by an increase in reduction temperature decreases the active sites of the material, which in turn leads to a decrease in catalyst activity.
FIG. 5 shows the polarization curves of HER-LSV of RuGa/C at different reduction temperatures in example 1 and those of comparative example 1 and comparative example 2, wherein the carbon-supported ruthenium simple substance (Ru/C) and the carbon-supported platinum simple substance (Pt/C) are characterized in that the material activity peaks and is superior to Ru/C and Pt/C when the reduction temperature is 600 ℃, which indicates that the catalytic activity of the material is improved by the introduction of gallium. The activity of the catalyst tends to decrease with increasing reduction temperature, because an increase in particle size caused by an increase in reduction temperature decreases the active sites of the material, which in turn leads to a decrease in catalyst activity.
FIG. 6 shows the reduction temperature of RuGa/C in example 1 and ruthenium dioxide (RuO) in comparative example 3 2 ) The OER-LSV polarization curve of (C) shows that the activity of the catalyst tends to decrease with increasing reduction temperature, and the material activity peaks and is superior to RuO when the reduction temperature is 600 DEG C 2 This indicates that the introduction of gallium promotes the catalytic activity of the material. The activity of the catalyst tends to decrease with increasing reduction temperature, because an increase in particle size caused by an increase in reduction temperature decreases the active sites of the material, which in turn leads to a decrease in catalyst activity.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The preparation method of the carbon-supported ruthenium-gallium intermetallic compound is characterized by comprising the following steps of:
(1) Dispersing ruthenium salt, gallium salt and a carbon carrier in a solvent, ultrasonically stirring, heating and evaporating the solvent, further drying the obtained solid product, and grinding to obtain precursor solid powder;
(2) And reducing the precursor solid powder in a reducing atmosphere to obtain the carbon-supported ruthenium-gallium intermetallic compound.
2. The method according to claim 1, wherein the temperature rise rate of the reduction step is 5 to 10 ℃/min, the reduction temperature is 600 to 800 ℃, and the reduction time is 2 to 10 hours.
3. The preparation method according to claim 1 or 2, wherein the mass fraction of ruthenium element in the precursor solid powder of step (1) is 15% to 20%.
4. The method according to claim 1 or 2, wherein the atomic ratio of ruthenium to gallium in the precursor solid powder of step (1) is 1: (0.5-1).
5. The method according to claim 1, wherein the ruthenium salt is at least one of ruthenium chloride, ruthenium acetylacetonate, and ruthenium acetate; the gallium salt is at least one of gallium nitrate, gallium acetate and gallium acetylacetonate.
6. The method according to claim 1, wherein the carbon carrier is at least one of carbon black, graphene, carbon nanotubes, and carbon nanowires.
7. The method according to claim 1, wherein the reducing atmosphere in the step (2) is an argon-hydrogen mixed gas, and the hydrogen gas volume ratio is 5% -10%.
8. The preparation method according to claim 1, wherein the solvent in the step (1) is at least one of water and ethanol, the ultrasonic stirring time is 0.5-2 h, and the heating temperature is 55-70 ℃.
9. A carbon-supported ruthenium-gallium intermetallic compound prepared according to any one of claims 1 to 8, wherein the carbon-supported ruthenium-gallium intermetallic compound is a pure phase ruthenium-gallium intermetallic compound.
10. Use of a carbon-supported ruthenium gallium intermetallic compound according to claim 9, wherein the use is for an alkaline anion exchange membrane fuel cell anode hydrogen oxidation reaction catalyst or an alkaline anion exchange membrane water electrolysis cell cathode hydrogen evolution and anode oxygen evolution reaction catalyst.
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