CN108355651B - Ruthenium nano metal electrocatalyst and preparation method thereof - Google Patents
Ruthenium nano metal electrocatalyst and preparation method thereof Download PDFInfo
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- CN108355651B CN108355651B CN201810127062.7A CN201810127062A CN108355651B CN 108355651 B CN108355651 B CN 108355651B CN 201810127062 A CN201810127062 A CN 201810127062A CN 108355651 B CN108355651 B CN 108355651B
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 73
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 69
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 22
- 239000002184 metal Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- -1 ruthenium phthalocyanine metal organic compound Chemical class 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002923 metal particle Substances 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
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- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
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- 229940048181 sodium sulfide nonahydrate Drugs 0.000 claims description 4
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 claims description 4
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- 230000000694 effects Effects 0.000 abstract description 7
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- 239000002994 raw material Substances 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 description 30
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- 238000011068 loading method Methods 0.000 description 7
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- 238000003795 desorption Methods 0.000 description 5
- 238000007619 statistical method Methods 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
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- 150000002894 organic compounds Chemical class 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 3
- 229920006391 phthalonitrile polymer Polymers 0.000 description 3
- 150000003303 ruthenium Chemical class 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- NTZMSBAAHBICLE-UHFFFAOYSA-N 4-nitrobenzene-1,2-dicarbonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C(C#N)=C1 NTZMSBAAHBICLE-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- 238000003917 TEM image Methods 0.000 description 2
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- GZQLDZZFNMLNEN-UHFFFAOYSA-N 3,4-dicyanobenzoic acid Chemical compound OC(=O)C1=CC=C(C#N)C(C#N)=C1 GZQLDZZFNMLNEN-UHFFFAOYSA-N 0.000 description 1
- MDXGRFMFORMPGT-UHFFFAOYSA-N 4-methylbenzene-1,2-dicarbonitrile Chemical compound CC1=CC=C(C#N)C(C#N)=C1 MDXGRFMFORMPGT-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
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- 229910000033 sodium borohydride Inorganic materials 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a ruthenium nanometer metal electrocatalyst and a preparation method thereof, wherein the preparation method of the ruthenium nanometer metal electrocatalyst comprises the following steps: preparing a ruthenium phthalocyanine metal organic compound; dispersing and mixing the ruthenium phthalocyanine metal organic compound and a two-dimensional carbon material to obtain an electrocatalyst precursor; and pyrolyzing the electrocatalyst precursor at high temperature in an inert atmosphere to obtain the ruthenium nanometer metal particle electrocatalyst. The method for preparing the electrocatalyst is simple, the raw material source is wide, particularly, the price of ruthenium is only about 5 percent of that of platinum, and the cost of the catalyst can be greatly reduced; the electrocatalyst has high HER activity in an acid-base solution and good stability, is particularly superior to a commercial Pt/C catalyst in an alkaline environment, and has good application prospect.
Description
Technical Field
The invention relates to the technical field of nano material electrocatalysis, in particular to a ruthenium nano metal electrocatalyst and a preparation method thereof.
Technical Field
With the rapid development of social economy, the rapid consumption of fossil energy and increasingly serious environmental pollution become major problems facing the world at present, and especially the haze problem in China has become the focus of public attention. Therefore, it is very urgent to find an alternative clean energy source. Hydrogen energy is an environmentally friendly clean energy, and is considered to be a sustainable clean energy which is most promising to replace petrochemical energy in the future due to the advantages of high energy density and zero pollution emission. At present, the content of hydrogen in the nature is very low, and the hydrogen can be prepared on a large scale only through various ways, wherein the electrolyzed water is a hydrogen production technology which is simple, has high hydrogen production purity and has industrial production value. The core problem faced by this technology is to develop an electrocatalyst with low cost, high activity and excellent stability, so as to reduce the energy consumed by the electrolysis of water to produce hydrogen.
Currently, noble metal platinum (Pt) is the best Hydrogen Evolution (HER) catalyst for electrolysis, but its wide application is limited due to high price and scarcity of Pt. Although the cost of the catalyst prepared by other alternative metals such as transition metals of iron, cobalt, nickel, molybdenum and the like is reduced, the activity and the stability of the catalyst in acid-base solution are far inferior to those of noble metal Pt, so that the catalyst cannot meet the requirements of industrial application.
Disclosure of Invention
Aiming at the problems of the prior HER catalyst, the invention provides a ruthenium nanometer metal particle electrocatalyst and a preparation method thereof.
The invention provides the following technical scheme:
a preparation method of a ruthenium nanometer metal electrocatalyst is characterized by comprising the following steps: the method comprises the following steps:
s1, preparing a ruthenium phthalocyanine metal organic compound;
s2, dispersing and mixing the ruthenium phthalocyanine metal organic compound and a two-dimensional carbon material to obtain an electrocatalyst precursor;
and S3, pyrolyzing the electrocatalyst precursor at high temperature in an inert atmosphere to obtain the ruthenium nanometer metal particle electrocatalyst.
Preferably, the ruthenium phthalocyanine-based organic compound in step S1 is prepared by mixing and reacting a metal ruthenium salt with phthalonitrile.
Preferably, the ruthenium salt is ruthenium trichloride.
Preferably, the phthalonitrile is at least one of 4-nitrophthalonitrile, 4-aminophthalic nitrile, 4-methylphthalonitrile or 4-carboxyphthalonitrile.
Preferably, the ruthenium phthalocyanine-based organic compound is prepared by reacting the metal ruthenium salt with phthalonitrile at 160 ℃ for 4 hours.
Preferably, the ruthenium phthalocyanine-based organic compound is tetraaminoruthenium phthalocyanine. Further preferably, the method for preparing the tetraaminoruthenium phthalocyanine comprises the following steps:
s11, mixing tetranitrophthalonitrile with ruthenium trichloride, uniformly stirring,
s12, heating the mixture obtained in the step S11 to 160 ℃, maintaining the temperature at 160 ℃ for reaction for 4 hours, naturally cooling to room temperature, grinding, and repeatedly extracting methanol and acetone to obtain 4-nitroruthenium phthalocyanine powder;
s13, mixing the 4-nitroruthenium phthalocyanine with sodium sulfide nonahydrate, adding N, N-dimethylformamide, reacting in a water bath at 60 ℃ for 8 hours, and filtering and extracting to obtain the 4-aminoruthenium phthalocyanine.
Preferably, the two-dimensional carbon material in step S2 is at least one of graphene oxide, graphene, or graphite-phase carbon nitride.
Preferably, in step S2, the mass ratio of the ruthenium phthalocyanine-based metal organic compound is 90 to 99 wt%, and the mass ratio of the two-dimensional carbon material is 1 to 10 wt%.
More preferably, the mass ratio of the two-dimensional carbon material is 5 wt%.
Preferably, the step S2 includes ultrasonically dispersing and mixing the ruthenium phthalocyanine metal organic compound and the two-dimensional carbon material in an aqueous solution, and then heating to evaporate water to obtain the electrocatalyst precursor.
Preferably, the step S3 includes putting the electrocatalyst precursor prepared in the step S2 into a tube furnace, raising the temperature at a rate of 2-10 ℃/min, and pyrolyzing at 500-1000 ℃ for 1-4 hours. Further preferably, the temperature is raised at a rate of 5 ℃/min and the pyrolysis is carried out at 800 ℃ for 2 hours.
The invention also provides a ruthenium nano metal electrocatalyst which is prepared by the preparation method of the ruthenium nano metal electrocatalyst.
Compared with the prior art, the invention has the beneficial effects that:
(1) the electrocatalyst obtained by the preparation method is a nitrogen-doped carbon-coated ruthenium nano metal electrocatalyst, the particle size of the metal ruthenium nano particles is small (1-3 nm), the ruthenium content is high (20-30 wt%), and the metal ruthenium nano particles are uniformly dispersed in a nitrogen-doped carbon skeleton without agglomeration and other phenomena, so the atom utilization rate of ruthenium metal is improved;
(2) the method for preparing the electrocatalyst is simple, the raw material source is wide, particularly, the price of ruthenium is only about 5 percent of that of platinum, and the cost of the catalyst can be greatly reduced;
(3) the electrocatalyst has high HER activity in an acid-base solution and good stability, is particularly superior to a commercial Pt/C catalyst in an alkaline environment, and has good application prospect.
Drawings
FIG. 1 is a schematic diagram of a synthetic route of a ruthenium phthalocyanine-based organometallic compound according to an embodiment of the present invention;
FIG. 2 is a schematic flow diagram illustrating the preparation of an electrocatalyst according to an embodiment of the invention;
FIG. 3 is a transmission electron micrograph of an electrocatalyst prepared in example 1 according to the present invention;
FIG. 4 is an elemental distribution diagram of an electrocatalyst prepared in example 1 of the present invention;
FIG. 5 is a scanning electron micrograph of an electrocatalyst prepared in example 1 according to the present invention;
FIG. 6 is an X-ray photoelectron spectrum of the electrocatalyst prepared in example 1 according to the present invention;
FIG. 7 shows a nitrogen desorption curve and a pore size distribution diagram of the electrocatalyst prepared in example 1 of the present invention;
FIG. 8 is a graph comparing the polarization curves of the electrocatalytic hydrogen evolution in alkaline solution for the catalysts of examples 1-3 of the present invention, and comparative examples 1-4;
FIG. 9 is a graph comparing the polarization curves of the electrocatalytic hydrogen evolution in an acidic solution for the catalysts of examples 1-3 of the present invention, and comparative examples 1-4;
FIG. 10 is a graph comparing the polarization curves of the electrocatalytic hydrogen evolution in neutral buffer solutions for the catalysts of examples 1-3 of the present invention, and comparative examples 1-4;
fig. 11a, 11b, 11c and 11d are graphs comparing initial polarization curves and polarization curves after 10000 CV (cyclic voltammetry) in an acid-base environment of the electrocatalyst prepared in examples 1-3 of the present invention and the catalyst of comparative example 4, respectively.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described with reference to the accompanying drawings and specific embodiments.
The invention provides a preparation method of a ruthenium nano-metal electrocatalyst, which comprises the following steps:
s1, preparing a ruthenium phthalocyanine metal organic compound;
s2, dispersing and mixing the ruthenium phthalocyanine metal organic compound and a two-dimensional carbon material to obtain an electrocatalyst precursor;
and S3, pyrolyzing the electrocatalyst precursor at high temperature in an inert atmosphere to obtain the ruthenium nanometer metal particle electrocatalyst.
It will be appreciated that, in the present invention, the precursor for preparing the electrocatalyst is a ruthenium phthalocyanine-based organometallic compound in which the metal ruthenium (Ru) is bonded by a chemical bond Ru-N4The ruthenium phthalocyanine is fixed at the central position of a phthalocyanine heterocyclic ring, and simultaneously, a two-dimensional carbon material is introduced to separate and separate the ruthenium phthalocyanine in space, and then the ruthenium phthalocyanine is pyrolyzed at high temperature under inert gas, so that the migration and aggregation of ruthenium (Ru) metal atoms are effectively controlled, the finally obtained ruthenium nano particles have small particle size (1-3 nm) and high ruthenium content (20-30 wt%), and therefore, more ruthenium active sites are exposed, and the obtained electrocatalyst has high catalytic activity and excellent stability and is far lower in cost than a Pt catalyst.
The invention also provides the following specific embodiments with reference to the attached drawings of the specification:
example 1
FIG. 1 is a schematic diagram showing the synthetic route of the ruthenium phthalocyanine metal organic compound of the present embodiment.
Specifically, 7.54g of tetranitrophthalonitrile was mixed with 2.25g of ruthenium trichloride (RuCl)3) Pouring into a three-neck flask, mechanically stirring and mixing uniformly, heating to 160 ℃ in an oil bath to enable reactants to be in a molten state, maintaining the temperature at 160 ℃ for reacting for 4 hours, naturally cooling to room temperature, grinding, and repeatedly extracting with methanol and acetone to obtain 4-nitroruthenium phthalocyanine (RuPc-NO)2) And (3) powder. Pouring 4.0g of 4-nitroruthenium phthalocyanine and 18g of sodium sulfide nonahydrate into a three-neck flask, adding 150mL of N, N-dimethylformamide, reacting in a water bath at 60 ℃ for 8 hours, and filtering and extracting to obtain 4-aminoruthenium phthalocyanine (RuPc-NH)2) (ii) a Dispersing the synthesized 4-aminoruthenium phthalocyanine (0.1g) in 20mL of water, adding 2.5mL of graphene oxide aqueous solution (2mg/mL), and performing ultrasonic dispersion treatment to obtain uniform ruthenium phthalocyanine/graphene oxide dispersion (RuPc-NH)2/GO) and then dried in a drying box at 80 ℃ to obtain RuPc-NH2a/GO mixture. Transferring the mixture as a precursor to a tube furnace for pyrolysis, wherein the pyrolysis conditions are as follows: under the argon atmosphere, the temperature rise range is 30-800 ℃, the speed is 5 ℃/min, and the temperature is maintained for 2 hours at 800 ℃. And after natural cooling, washing with ethanol to obtain the electrocatalyst Ru @ NG. In the catalyst, ruthenium atoms in ruthenium phthalocyanine are reduced at high temperature to form ruthenium nanoparticles, nitrogen and carbon elements are converted into nitrogen-doped carbon materials, and graphene oxide is reduced at high temperature to form nitrogen-doped graphene materials. Through the statistical analysis of TEM photos, the particle size distribution of the ruthenium nanoparticles is 1.03 +/-0.23 nm. According to an EDX test, the mass fraction of ruthenium is 25.3 wt%, the mass fraction of nitrogen is 4.5 wt% and the mass fraction of carbon is 70.2 wt%. Thermogravimetric analysis showed a Ru content of 23.7 wt%. Nitrogen adsorption and desorption tests show that the catalyst has the thickness of 73.9m2g-1Pore volume was 0.17cm3g-1The average pore diameter was 2.73 nm.
In the electrocatalytic hydrogen evolution test, the electrocatalyst Ru @ NG prepared in this example 1 employs a three-electrode system, that is, the working electrode is a glassy carbon electrode (diameter 3mm), the graphite rod is a counter electrode, Ag/AgCl (saturated potassium chloride solution) is a reference electrode, and the loading amount of the electrocatalyst is 0.8mg · cm-2The electrolyte is 1.0M KOH respectively，0.5M H2SO41.0M PB buffer. The results of the electrocatalytic hydrogen evolution performance are shown in fig. 8, 9, 10 and 11.
Example 2
4-aminoruthenium phthalocyanine (RuPc-NH) synthesized in example 12) Directly transferring the precursor into a tube furnace for pyrolysis. Pyrolysis conditions are as follows: under the argon atmosphere, the temperature rise range is 30-800 ℃, the speed is 5 ℃/min, and the temperature is maintained for 2 hours at 800 ℃. And after natural cooling, washing with ethanol to obtain the electrocatalyst Ru @ NC. In the catalyst, ruthenium atoms in ruthenium phthalocyanine are reduced at high temperature to form ruthenium nanoparticles, and nitrogen and carbon elements are converted into nitrogen-doped carbon materials. Through the statistical analysis of the TEM photograph, the particle size distribution of the ruthenium nano-particles is 1.44 +/-0.36 nm. Thermogravimetric analysis showed a Ru content of 26.5 wt%. The nitrogen adsorption and desorption test shows that the catalyst has the diameter of 55.7m2g-1Pore volume was 0.18cm3g-1The average pore diameter was 2.73 nm.
In the electrocatalytic hydrogen evolution test, the electrocatalyst Ru @ NC prepared in this example 2 employs a three-electrode system, that is, the working electrode is a glassy carbon electrode (diameter 3mm), the graphite rod is a counter electrode, Ag/AgCl (saturated potassium chloride solution) is a reference electrode, and the loading amount of the electrocatalyst is 0.8mg · cm-2The electrolyte is 1.0M KOH, 0.5M H2SO41.0M PB buffer. The results of the electrocatalytic hydrogen evolution performance are shown in fig. 8, 9, 10 and 11.
FIG. 2 is a schematic diagram showing the processes of the electrocatalyst Ru @ NG prepared in example 1 and the electrocatalyst Ru @ NC prepared in example 2 according to the present invention, which shows the presence of ruthenium nanoparticles in Ru-N4The formation process under the chemical anchoring effect and the physical barrier effect of the graphene two-dimensional material is effectively prevented from aggregation of ruthenium nanoparticles.
Example 3
The 4-aminoruthenium phthalocyanine (0.1g) synthesized in example 1 was dispersed in 20mL of water, and graphite-phase carbon nitride nanosheets (g-C) obtained by ultrasonic exfoliation were added3N4)2.5mL of aqueous solution (2mg/mL) is subjected to ultrasonic dispersion treatment to obtain uniform ruthenium phthalocyanine/graphite phase carbon nitride dispersion liquid (RuPc-NH)2/g-C3N4) Then dried in a drying oven at 80 ℃ to obtain RuPc-NH2/g-C3N4And (3) mixing. Transferring the mixture as a precursor to a tube furnace for pyrolysis, wherein the pyrolysis conditions are as follows: under the argon atmosphere, the temperature rise range is 30-800 ℃, the speed is 5 ℃/min, and the temperature is maintained for 2 hours at 800 ℃. After natural cooling, the electrocatalyst Ru @ N-g-CN is obtained after ethanol cleaning. In the catalyst, ruthenium atoms in ruthenium phthalocyanine are reduced at high temperature to form ruthenium nanoparticles, nitrogen and carbon elements are converted into nitrogen-doped carbon materials, and graphite-phase carbon nitride is converted into nitrogen-doped graphite materials at high temperature. Through the statistical analysis of TEM photos, the particle size distribution of the ruthenium nano particles is 1.24 +/-0.27 nm. Thermogravimetric analysis showed a Ru content of 28.5 wt%. Nitrogen adsorption and desorption tests show that the catalyst has the particle size of 58.4m2g-1Pore volume was 0.16cm3g-1The average pore diameter was 3.4 nm.
In the electrocatalytic hydrogen evolution test, the electrocatalyst Ru @ N-g-CN prepared in the embodiment 3 adopts a three-electrode system, namely, a working electrode is a glassy carbon electrode (with the diameter of 3mm), a graphite rod is a counter electrode, Ag/AgCl (saturated potassium chloride solution) is a reference electrode, and the loading capacity of the electrocatalyst is 0.8mg cm-2The electrolyte is 1.0M KOH, 0.5M H2SO4 and 1.0M PB buffer respectively. The results of the electrocatalytic hydrogen evolution performance are shown in fig. 8, 9, 10 and 11.
Comparative example 1
Directly weighing 1.04g of 4-nitrophthalonitrile and 0.3g of ruthenium trichloride, grinding the mixture, and transferring the mixture serving as a precursor into a tubular furnace for pyrolysis under the pyrolysis conditions: under the argon atmosphere, the temperature rise range is 30-800 ℃, the speed is 5 ℃/min, and the temperature is maintained for 2 hours at 800 ℃. After natural cooling, the electrocatalyst Ru/CN is obtained after ethanol cleaning. In the catalyst, ruthenium atoms in ruthenium trichloride are subjected to high-temperature thermal reduction and aggregation to form ruthenium nanoparticles, and nitrogen and carbon elements are converted into nitrogen-doped carbon materials. Through the statistical analysis of TEM photos, the particle size distribution of the ruthenium nano-particles is very wide, and obvious agglomeration phenomenon of ruthenium metal occurs. Thermogravimetric analysis showed a Ru content of 28.5 wt%.
Electrocatalysts Ru/NC prepared in this comparative example 1 were precipitated by electrocatalysisIn the hydrogen test, a three-electrode system is adopted, namely a working electrode is a glassy carbon electrode (with the diameter of 3mm), a graphite rod is a counter electrode, Ag/AgCl (saturated potassium chloride solution) is a reference electrode, and the loading capacity of an electrocatalyst is 0.8mg cm-2The electrolyte is 1.0M KOH, 0.5M H2SO41.0M PB buffer. The electrocatalytic hydrogen evolution performance results are shown in fig. 8, 9, 10.
Comparative example 2
0.1g of sodium borohydride (NaBH) is weighed out4) Dissolved in 20mL of deionized water, and ruthenium trichloride (5mg mL) was slowly added dropwise with vigorous stirring-1) 20mL of the aqueous solution is stirred at room temperature for 20 hours, then the mixture is kept stand, and after centrifugation and ethanol washing, the metal ruthenium nanoparticles (Ru-np) are obtained.
In the electrocatalytic hydrogen evolution test, the electrocatalyst Ru-np prepared in the comparative example 2 adopts a three-electrode system, namely a working electrode is a glassy carbon electrode (the diameter is 3mm), a graphite rod is a counter electrode, Ag/AgCl (saturated potassium chloride solution) is a reference electrode, and the loading capacity of the electrocatalyst is 0.8mg cm-2The electrolyte is 1.0M KOH, 0.5M H2SO41.0M PB buffer. The electrocatalytic hydrogen evolution performance results are shown in fig. 8, 9, 10.
Comparative example 3
7.54g of tetranitrophthalonitrile were reacted with 3.0 g of zinc chloride (ZnCl)2) Pouring into a three-neck flask, mechanically stirring and mixing uniformly, heating to 160 ℃ in an oil bath to enable reactants to be in a molten state, maintaining the temperature at 160 ℃ for reaction for 4 hours, naturally cooling to room temperature, grinding, and repeatedly extracting with methanol and acetone to obtain 4-nitrozinc phthalocyanine powder (ZnPc-NO)2). 4.0g of ZnPc-NO2Pouring the mixture and 18g of sodium sulfide nonahydrate into a three-neck flask, adding 150mL of N, N dimethylformamide, reacting in water bath at 60 ℃ for 8 hours, and filtering and extracting to obtain 4-amino zinc phthalocyanine (ZnPc-NH)2) (ii) a Reacting ZnPc-NH2Transferring the precursor into a tube furnace for pyrolysis, wherein the pyrolysis conditions are as follows: under the argon atmosphere, the temperature rise range is 30-800 ℃, the speed is 5 ℃/min, and the temperature is maintained for 2 hours at 800 ℃. And naturally cooling, and washing with ethanol to obtain the electrocatalyst NC. In the catalyst, zinc atoms in the zinc phthalocyanine are reduced at high temperature to form metal zinc and evaporated to disappear, and nitrogenAnd the carbon element is converted into a nitrogen-doped carbon material.
In the electrocatalytic hydrogen evolution test, the electrocatalyst NC prepared in the comparative example 3 adopts a three-electrode system, namely a working electrode is a glassy carbon electrode (diameter is 3mm), a graphite rod is a counter electrode, Ag/AgCl (saturated potassium chloride solution) is a reference electrode, and the loading capacity of the electrocatalyst is 0.8 mg-cm-2The electrolyte is 1.0M KOH, 0.5M H2SO41.0M PB buffer. The results of the electrocatalytic hydrogen evolution performance are shown in fig. 8, 9 and 10.
Comparative example 4
Commercial Pt/C (20 wt%) catalyst from Johnson Matthey was purchased for comparison in an electrocatalytic hydrogen evolution test. The test adopts a three-electrode system, namely a working electrode is a glassy carbon electrode (with the diameter of 3mm), a graphite rod is a counter electrode, Ag/AgCl (saturated potassium chloride solution) is a reference electrode, and the loading capacity of an electrocatalyst is 0.8mg cm-2The electrolyte is 1.0M KOH, 0.5M H2SO41.0M PB buffer. The results of the electrocatalytic hydrogen evolution performance are shown in fig. 8, 9, 10 and 11.
Analysis of results
FIG. 3 is a transmission electron micrograph of an electrocatalyst obtained in example 1; as can be seen from the figure, in the electrocatalyst (Ru @ NG) prepared in example 1, Ru nanoparticles are uniformly distributed in the carbon-based framework, and no obvious Ru nano macroparticles exist; the diameter of Ru in the catalyst is about 1.03nm +/-0.23 nm through particle size statistical analysis; it was demonstrated that agglomeration of Ru metal can be avoided using the method of example 1, thereby ensuring sufficient exposure of catalytically active sites.
FIG. 4 is an elemental distribution diagram of the electrocatalyst prepared in example 1; from the figure, it can be confirmed that the catalyst Ru @ NG prepared in example 1 has the presence and uniform distribution of the three elements Ru, C and N.
FIG. 5 is a scanning electron micrograph of an electrocatalyst prepared in example 1; as can be seen from the figure, the morphology of the catalyst Ru @ NG prepared in example 1 at the micrometer scale is a porous structure, which is beneficial to increasing the active area of the catalyst and the exposed number of active sites, so that the catalytic performance is improved.
FIG. 6 is an X-ray photoelectron spectrum of the electrocatalyst prepared in example 1; as can be seen from the figure, the catalyst Ru @ NG prepared in example 1 has a four-element composition (Ru, C, N and O), where O is primarily responsible for oxygen, moisture, etc. physically adsorbed by the catalyst.
FIG. 7 is a nitrogen adsorption/desorption curve and a pore size distribution diagram of the electrocatalyst prepared in example 1; as can be seen from the figure, the Ru @ NG nitrogen adsorption and desorption curve of the catalyst prepared in example 1 is the fourth type of potential, and the pore size of the catalyst is within 10nm, which proves that the catalyst is of a porous structure, so that the catalytic performance is favorably improved.
FIG. 8 is a graph comparing the polarization curves of electrocatalytic hydrogen evolution in alkaline solution for the catalysts of examples 1-3, and comparative examples 1-4; as can be seen from the figure, the catalysts Ru @ NG, Ru @ NC and Ru @ N-g-CN prepared in examples 1,2 and 3 have excellent hydrogen evolution properties at 10mA cm-2The overpotentials at current densities were 20,19,25mV, respectively, which is superior to the commercial Pt/C catalyst of comparative example 4, as well as significantly superior to the Ru/NC, Ru-np, and NC catalysts prepared in comparative examples 1,2, 3. At high current densities, e.g. 50mA cm-2The overpotential for the catalyst Ru @ NG prepared in example 1 was very small, only 74 mV.
FIG. 9 is a graph comparing the polarization curves of electrocatalytic hydrogen evolution in acidic solution for the catalysts of examples 1-3, and comparative examples 1-4; as can be seen from the figure, the catalysts Ru @ NG, Ru @ NC and Ru @ N-g-CN prepared in examples 1,2 and 3 also have excellent hydrogen evolution properties at 10mA cm-2The overpotentials at current densities were 43,43,55mV, respectively, slightly lower than the commercial Pt/C catalyst of comparative example 4, but better than the Ru/NC, Ru-np, and NC catalysts prepared in comparative examples 1,2, 3.
FIG. 10 is a graph comparing the electrocatalytic hydrogen evolution polarization curves of the catalysts of examples 1-3, and comparative examples 1-4 in neutral buffer solution; as can be seen from the figure, the catalysts Ru @ NG, Ru @ NC and Ru @ N-g-CN prepared in examples 1,2 and 3 have significantly reduced hydrogen evolution properties compared to those obtained in alkaline or acidic environments, which are mainly due to the slow hydrolysis kinetics in neutral solution. At 10mA cm-2Overpotential partial pressure at current densityThe other was 128,144,165mV, lower than the commercial Pt/C catalyst of comparative example 4, but better than the Ru/NC, Ru-np, and NC catalysts prepared in comparative examples 1,2, 3.
FIGS. 11a, 11b, 11C and 11d are graphs comparing the initial polarization curves of the electrocatalysts prepared in examples 1 to 3 and the Pt/C catalyst of comparative example 4 in an acid-base environment with the polarization curves after 10000 CV (cyclic voltammetry), respectively. As can be seen from the figure, the LSV curve of the catalyst Ru @ NG prepared in example 1 has almost no obvious shift after long-time circulation in acid-base environment, which indicates that the catalyst has excellent stability in acid and base environments; similarly, the catalysts Ru @ NC and Ru @ N-g-CN prepared in examples 2 and 3 also have excellent stability in an acid-base environment, but the LSV curve displacement after the CV cycling is 10000 times is slightly increased compared with that of the Ru @ NG catalyst, presumably because the introduction of the graphene is easier to wrap and protect Ru nanoparticles and prevent corrosion of acid-base solution. The Pt/C catalyst of comparative example 4 showed good stability under acidic conditions, but the LSV curve clearly showed negative electrode shift after CV cycling 10000 times under alkaline conditions, indicating that the Pt/C catalyst was slightly less stable under alkaline conditions.
The comparison of the test results shows that the ruthenium nano metal electrocatalyst prepared by the preparation method of the invention has high HER activity in acid-base solution and good stability, and is particularly superior to a commercial Pt/C catalyst in an alkaline environment.
The present invention also provides a ruthenium nanometal electrocatalyst which can be prepared as described in the preparation method of the ruthenium nanometal electrocatalyst in examples 1 to 3 above.
In the description of the embodiments of the invention, the particular features, structures, materials, or characteristics may be combined in any suitable manner in any one or more embodiments or examples.
In the description of the embodiments of the present invention, it should be understood that "-" and "-" indicate the same range of two numerical values, and the range includes the endpoints. For example, "A-B" means a range greater than or equal to A and less than or equal to B. "A to B" means a range of not less than A and not more than B.
In the description of the embodiments of the present invention, the term "and/or" herein is only one kind of association relationship describing an associated object, and means that there may be three kinds of relationships, for example, a and/or B, and may mean: a exists alone, A and B exist simultaneously, and B exists alone. In addition, the character "/" herein generally indicates that the former and latter related objects are in an "or" relationship.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. A preparation method of a ruthenium nanometer metal electrocatalyst is characterized by comprising the following steps: the method comprises the following steps:
s1, preparing a ruthenium phthalocyanine metal organic compound;
s2, dispersing and mixing the ruthenium phthalocyanine metal organic compound and a two-dimensional carbon material to obtain an electrocatalyst precursor;
s3, pyrolyzing the electrocatalyst precursor at high temperature in an inert atmosphere to obtain the ruthenium nanometer metal particle electrocatalyst;
the ruthenium phthalocyanine metal organic compound is 4-aminoruthenium phthalocyanine, and the preparation method of the 4-aminoruthenium phthalocyanine comprises the following steps:
s11, mixing tetranitrophthalonitrile with ruthenium trichloride, uniformly stirring,
s12, heating the mixture obtained in the step S11 to 160 ℃, maintaining the temperature at 160 ℃ for reaction for 4 hours, naturally cooling to room temperature, grinding, and repeatedly extracting methanol and acetone to obtain 4-nitroruthenium phthalocyanine powder;
s13, mixing the 4-nitroruthenium phthalocyanine with sodium sulfide nonahydrate, adding N, N-dimethylformamide, reacting in a water bath at 60 ℃ for 8 hours, and filtering and extracting to obtain the 4-aminoruthenium phthalocyanine.
2. The method of claim 1, wherein the two-dimensional carbon material in step S2 is at least one of graphene oxide, graphene, or graphite-phase carbon nitride.
3. The method of claim 1, wherein in step S2, the mass ratio of the ruthenium phthalocyanine metal organic compound is 90-99 wt%, and the mass ratio of the two-dimensional carbon material is 1-10 wt%.
4. The method of claim 1, wherein the precursor is pyrolyzed at a high temperature in a tube furnace in the step S3 at a temperature ranging from room temperature to a target temperature of 500-1000 ℃, at a temperature rising rate of 2-10 ℃/min, and at the set target temperature for 1-4 hours.
5. A ruthenium nanometal electrocatalyst prepared by the method for preparing a ruthenium nanometal electrocatalyst according to any one of claims 1 to 4.
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