CN110860301B - Ruthenium phosphide-loaded carbon micron sheet dual-functional electrocatalyst, preparation method thereof and application of dual-functional electrocatalyst in efficient electrolytic hydrogen production - Google Patents
Ruthenium phosphide-loaded carbon micron sheet dual-functional electrocatalyst, preparation method thereof and application of dual-functional electrocatalyst in efficient electrolytic hydrogen production Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 63
- 239000001257 hydrogen Substances 0.000 title claims abstract description 63
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 50
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims description 18
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- 238000004519 manufacturing process Methods 0.000 title abstract description 32
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- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims description 9
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- LWFBRHSTNWMMGN-UHFFFAOYSA-N 4-phenylpyrrolidin-1-ium-2-carboxylic acid;chloride Chemical compound Cl.C1NC(C(=O)O)CC1C1=CC=CC=C1 LWFBRHSTNWMMGN-UHFFFAOYSA-N 0.000 claims description 4
- CEDDGDWODCGBFQ-UHFFFAOYSA-N carbamimidoylazanium;hydron;phosphate Chemical compound NC(N)=N.OP(O)(O)=O CEDDGDWODCGBFQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 abstract description 46
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 abstract description 46
- 238000007254 oxidation reaction Methods 0.000 abstract description 46
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
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- 150000003303 ruthenium Chemical class 0.000 description 9
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- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- VNKBTWQZTQIWDV-UHFFFAOYSA-N azamethiphos Chemical compound C1=C(Cl)C=C2OC(=O)N(CSP(=O)(OC)OC)C2=N1 VNKBTWQZTQIWDV-UHFFFAOYSA-N 0.000 description 3
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- 239000007772 electrode material Substances 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- B01J35/60—
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
-
- B01J35/33—
-
- B01J35/393—
-
- 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
-
- 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
- B01J37/084—Decomposition of carbon-containing compounds into 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
-
- 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
-
- 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 provides a ruthenium phosphide-loaded carbon micron sheet dual-functional electrocatalyst which is a composite structure of ruthenium phosphide nano-particles and carbon micron sheets. The nano-sheets constitute a loose porous structure. The bifunctional electrocatalyst can be simultaneously used for electrocatalytic oxidation and water electrolytic reduction of small molecular hydrazine hydrate, and replaces the traditional electrochemical oxygen evolution reaction with hydrazine hydrate oxidation with low thermodynamic potential, so that a two-electrode electrolytic system is constructed, and low-energy-consumption and stable electrochemical hydrogen production is realized.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to preparation of a ruthenium phosphide-loaded carbon micron sheet dual-functional electrocatalyst and application of the electrocatalyst in efficient electrolytic hydrogen production.
Background
The method for producing hydrogen by electrolyzing water is an ideal method for preparing high-purity hydrogen, however, due to the anode slow four-electron reaction, the commercialized electrolyzed water usually needs to overcome 600-800 mV overpotential to effectively produce hydrogen, and the stability is poor, meanwhile, the currently reported good hydrogen production and oxygen production catalysts are respectively realized under acidic and alkaline conditions, and the complexity and the cost of an electrolyzed water device are increased, so that the oxidation reaction with low thermodynamic potential is adopted to replace the water oxidation reaction with slow dynamics, and the method is an effective way for reducing energy consumption and improving the hydrogen production efficiency. Hydrazine hydrate is used as a low-cost fuel with high energy density, and can be oxidized at low potential (thermodynamic potential: -0.33V vs RHE) to release N2And water, while avoiding the generation of catalyst poisoning species resulting from the oxidation of other organics. Therefore, hydrazine hydrate oxidation-assisted hydrogen production is an efficient hydrogen production strategy, but related reports are few at present.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a preparation method of a ruthenium phosphide-loaded carbon micron bifunctional electrocatalyst and an application of the electrocatalyst in efficient electrolytic hydrogen production.
The invention provides a ruthenium phosphide-loaded carbon micron sheet dual-functional electrocatalyst which is a composite structure of ruthenium phosphide nano-particles and carbon micron sheets.
Preferably, the particle size of the ruthenium phosphide nano-particles is 5-20 nm.
Preferably, the nanomaterial is a loose porous structure.
The invention also provides a preparation method of the ruthenium phosphide-loaded carbon micron sheet bifunctional electrocatalyst, which comprises the following steps:
mixing ruthenium salt and an organic phosphorus source compound, and calcining under a protective atmosphere condition to obtain the ruthenium phosphide-loaded carbon micron sheet dual-functional electrocatalyst.
Preferably, the ruthenium salt is selected from ruthenium trichloride.
Preferably, the organophosphorus source compound is selected from one or more of melamine phosphate, azamethiphos, guanidine phosphate and guanylurea phosphate.
Preferably, the molar ratio of the ruthenium salt to the organic phosphorus source compound is 1: 5-1: 20.
Preferably, the calcination conditions are as follows: heating to 850-900 ℃ at the heating rate of 2-20 ℃/min and calcining for 2-4 h.
Preferably, the protective atmosphere condition is argon-hydrogen mixed gas or argon gas.
The invention also provides an application of the ruthenium phosphide-loaded carbon micron sheet bifunctional electrocatalyst in hydrazine hydrate oxidation-assisted hydrogen production.
Compared with the prior art, the invention provides the ruthenium phosphide-loaded carbon micron sheet dual-functional electrocatalyst which is a composite structure of ruthenium phosphide nano-particles and carbon micron sheets. The nano-sheets form a loose porous structure. The bifunctional electrocatalyst can be simultaneously used for electrocatalytic oxidation and water electrolytic reduction of small-molecular hydrazine hydrate to produce hydrogen, and meanwhile, hydrazine hydrate oxidation with low thermodynamic potential replaces the traditional electrochemical oxygen evolution reaction to construct a two-electrode electrolytic system and realize low-energy-consumption and stable electrochemical hydrogen production.
The results show that the current density of the bifunctional electrocatalyst is 10mA/cm in 1.0M KOH2When the corresponding hydrogen evolution potential is-0.025V, at 1.0M KOH +0.3M N2H4The medium current density is 10mA/cm2The oxidation potential of the corresponding hydrazine hydrate is-0.07V at 1.0M KOH +0.3M N2H4The medium current density is 10mA/cm2The voltage of the auxiliary hydrogen production by hydrazine hydrate electrolysis is 0.023V, which is obviously less than the voltage of the relevant electrolyzed water, and the method has good stability and is easy for large-scale production.
Drawings
FIG. 1 is a topographical view of the target product obtained in example 1;
FIG. 2 is a phase diagram of the target product obtained in example 1;
FIG. 3 is an X-ray photoelectron spectrum of the target product obtained in example 1;
FIG. 4 is a graph showing the electrocatalytic hydrogen evolution and hydrazine hydrate oxidation performance of the target product obtained in example 1;
FIG. 5 is a diagram showing the performance of hydrazine hydrate oxidation-assisted hydrogen production and full hydrolysis of the target product obtained in example 1;
FIG. 6 is a diagram showing the morphology and phase of the target product obtained in example 2;
FIG. 7 is a graph showing the electrocatalytic hydrogen evolution and hydrazine hydrate oxidation performance of the target product obtained in example 2;
FIG. 8 is a diagram showing the morphology and phase of the target product obtained in example 3;
FIG. 9 is a graph showing the electrocatalytic hydrogen evolution and hydrazine hydrate oxidation performance of the target product obtained in example 3;
FIG. 10 is a diagram showing the morphology and phase of the target product obtained in example 4;
FIG. 11 is a graph showing electrocatalytic hydrogen evolution and hydrazine hydrate oxidation performances of the target product obtained in example 4;
FIG. 12 is a diagram showing the morphology and phase of the target product obtained in example 5;
FIG. 13 is a graph showing electrocatalytic hydrogen evolution and hydrazine hydrate oxidation performance of the target product obtained in example 5;
FIG. 14 is a diagram showing the morphology and phase of the target product obtained in example 6;
FIG. 15 is a graph showing electrocatalytic hydrogen evolution and hydrazine hydrate oxidation performances of the target product obtained in example 6;
FIG. 16 is a diagram showing the morphology and phase of the target product obtained in example 7;
FIG. 17 is a graph showing electrocatalytic hydrogen evolution and hydrazine hydrate oxidation performance of the target product obtained in example 7;
FIG. 18 is a diagram showing the morphology and phase of the target product obtained in example 8;
FIG. 19 is a diagram showing the morphology and phase of the target product obtained in example 9;
FIG. 20 is a diagram showing the morphology and phase of the target product obtained in example 10;
FIG. 21 is a diagram showing the morphology and phase of the target product obtained in example 11;
FIG. 22 is a diagram showing the morphology and phase of the target product obtained in example 12;
FIG. 23 is a diagram showing the morphology and phase of the target product obtained in example 13;
FIG. 24 is a graph showing electrocatalytic hydrogen evolution and hydrazine hydrate oxidation performances of the objective product obtained in example 13;
FIG. 25 is a diagram showing the morphology and phase of the target product obtained in example 14;
FIG. 26 is a graph showing electrocatalytic hydrogen evolution and hydrazine hydrate oxidation performances of the objective product obtained in example 14.
Detailed Description
The invention provides a ruthenium phosphide-loaded carbon micron sheet dual-functional electrocatalyst which is a composite structure of ruthenium phosphide nano-particles and carbon micron sheets.
In some embodiments of the invention, the bifunctional electrocatalyst is ruthenium phosphide nanoparticles supported on the surface of carbon micron sheets.
In some embodiments of the invention, the bifunctional electrocatalyst is a ruthenium phosphide nanoparticle embedded carbon micro-platelet layer.
The particle size of the ruthenium phosphide nano-particles is 5-20 nm.
The overall appearance of the bifunctional electrocatalyst is a loose and porous micron sheet structure.
The invention also provides a preparation method of the ruthenium phosphide-loaded carbon micron sheet bifunctional electrocatalyst, which comprises the following steps:
mixing ruthenium salt and an organic phosphorus source compound, and calcining under a protective atmosphere condition to obtain the ruthenium phosphide-loaded carbon micron sheet dual-functional electrocatalyst.
Firstly, ruthenium salt and an organic phosphorus source compound are mixed to obtain a precursor.
The mixing mode is not particularly limited, and the mixing mode can be dry mixing, namely, the ruthenium salt and the organic phosphorus source compound are directly mixed and then ground to obtain a precursor;
or dispersing and mixing ruthenium salt and an organic phosphorus source compound in a solvent, centrifugally separating, and drying to obtain the precursor. Among them, the solvent is preferably ethanol.
The ruthenium salt is selected from ruthenium trichloride.
The organic phosphorus source compound is selected from one or more of melamine phosphate, azamethiphos, guanidine phosphate and guanylurea phosphate, and is preferably melamine phosphate.
The molar ratio of the ruthenium salt to the organic phosphorus source compound is 1: 5-1: 20, and preferably 1: 10-1: 15.
And then, calcining the precursor under the condition of protective atmosphere to obtain the ruthenium phosphide supported carbon micron sheet bifunctional electrocatalyst.
Wherein the calcining conditions are as follows: heating to 850-900 ℃ at a heating rate of 2-20 ℃/min, preferably 2-10 ℃/min, and calcining for 2-4 h.
The protective atmosphere condition is argon-hydrogen mixed gas or argon gas, wherein the volume percentage of hydrogen in the argon-hydrogen mixed gas is 10%.
Compared with the prior art, the invention has the following advantages and beneficial results:
(1) the preparation method consists of simple adsorption and calcination, and has the advantages of simple steps, strong operability and easy repetition.
(2) The material is a high-dispersion nanoscale ruthenium phosphide-loaded carbon micron sheet dual-functional electrode material, wherein the nano particles are between 5 and 20nm, and the nano sheets have porous structures.
(3) The highly dispersed nano ruthenium phosphide-loaded carbon micron sheet has excellent electrochemical hydrogen production and hydrazine hydrate oxidation performances, and reaches 10mA/cm in 1.0M KOH2The potential required for the current density of (1.0M KOH +0.3M N) is only-0.025V2H4The medium current density is 10mA/cm2The oxidation potential of the corresponding hydrazine hydrate is-0.071V at 1.0M KOH +0.3M N2H4The medium current density is 10mA/cm2The voltage of the corresponding hydrazine hydrate oxidation auxiliary hydrogen production is 0.023V.
(4) The invention is based on the chemical coupling of the highly dispersed ruthenium phosphide nano-particles and the carbon micron sheet, improves the electronic structure of the material, increases the number of active sites, is beneficial to the permeation of electrolyte and the release of gas due to the existence of a large number of macroporous and mesoporous structures, and synergistically improves the electrocatalytic activity and stability of the material.
For further understanding of the present invention, the following examples are provided to illustrate the preparation of the ruthenium phosphide-supported carbon micron sheet bifunctional electrocatalyst and the application of high-efficiency electrolytic hydrogen production, and the scope of the present invention is not limited by the following examples.
Example 1
The ruthenium source is ruthenium trichloride, the organic carbon source is melamine phosphate, and the molar ratio is 1:15.
(1) Dispersing ruthenium trichloride and melamine phosphate in ethanol at a molar ratio of 1:15, stirring for 30min, centrifuging at 8000rpm for 2min, and drying at 80 ℃ overnight to obtain a precursor.
(2) And (3) placing the precursor in the step (1) in a tube furnace, heating to 850 ℃ at the speed of 2 ℃/min in argon-hydrogen mixed atmosphere with the volume content of hydrogen of 10%, keeping for 2h, and naturally cooling to room temperature to obtain the target product.
The hydrogen evolution and hydrazine hydrate oxidation performance adopts a three-electrode system, a glassy carbon electrode with the diameter of 3mm is adopted as a working electrode, a graphite rod electrode is adopted as a counter electrode, a mercury/mercury oxide electrode is adopted as a reference electrode, and the electrolyte is 1.0M KOH or 1.0M KOH +0.3M N2H4The sweep rate of the polarization curve was 5 mV/s.
Hydrazine hydrate oxygenThe chemical auxiliary hydrogen production adopts a two-electrode system, and the electrolyte is 1.0M KOH +0.3M N2H4The sweep rate of the polarization curve was 5mV/s, and the voltage applied for the timer current was 0.023V.
FIG. 1 shows the morphology of the target product obtained in example 1, A and B are scanning electron micrographs of the target product obtained in example 1, and C and D are transmission electron micrographs of the target product obtained in example 1.
The figure shows that the synthesized material is a loose porous structure formed by loading ruthenium phosphide nanoparticles on the surface of a carbon micron sheet and the ruthenium phosphide nanoparticles, wherein the crystallinity of the ruthenium phosphide nanoparticles is good, and the average particle size is about 9.44 nm.
FIG. 2 shows a phase diagram of the target product obtained in example 1, wherein A is an X-ray diffraction diagram and B is a Raman spectrum. The figure shows that the synthesized material is a composite of ruthenium phosphide and carbon, wherein the graphitization degree of the carbon is better.
FIG. 3 shows the chemical elements and surface valence states of the target product obtained in example 1, from which it can be seen that C, N, P and Ru both exist.
FIG. 4 is a diagram showing the electrocatalytic hydrogen evolution and hydrazine hydrate oxidation performance of the target product obtained in example 1, wherein A is a diagram showing the hydrogen production performance by electrolyzed water, and B is a diagram showing the hydrazine hydrate oxidation performance. As can be seen from the figure, the catalyst has excellent hydrogen evolution performance and hydrazine hydrate oxidation performance in alkaline, and the current density is 10mA/cm in 1.0M KOH2The potential is only-0.025V, which is obviously better than the commercial 20 wt% Pt/C (-0.036V); at 1.0M KOH +0.3M N2H4In the range of 10mA/cm in current density2The potential at this time was only-0.071V, significantly lower than the commercial 20 wt% Pt/C (0.131V).
Fig. 5 is a graph showing the performance of hydrazine hydrate oxidation-assisted hydrogen production and total hydrolysis of the target product obtained in example 1, wherein a is a graph showing the performance of hydrazine hydrate oxidation-assisted hydrogen production and total hydrolysis, B is a graph showing the performance of example 1 and commercial Pt/C, C is a timing current graph, and D is a hydrogen yield graph. As can be seen from the figure, the polarization curve of hydrazine hydrate oxidation-assisted hydrogen production is obviously shifted negatively relative to the total hydrolysis, and the current density can reach 10mA/cm only by the voltage of 0.023V2Whereas commercial 20 wt% Pt/C requires 0.117V to achieve the same current density.Constant potential test shows that the current density can be kept stable within 20h, and the hydrogen production is linearly increased within 75min and is close to the theoretical value.
Example 2
The procedure is as in example 1, except that the molar ratio of ruthenium trichloride to melamine phosphate is 1: 5.
FIG. 6 is a diagram showing the morphology and phase of the target product obtained in example 2, wherein A is a transmission electron microscope diagram of the target product obtained in example 2, and B is an XRD diagram of the target product obtained in example 2. The figure shows that the synthesized material is a loose porous structure formed by loading ruthenium phosphide nano-particles on the surface of a carbon micron sheet and the carbon micron sheet.
FIG. 7 is a graph showing the electrocatalytic hydrogen evolution and hydrazine hydrate oxidation performance of the target product obtained in example 2, wherein A is a graph showing the hydrogen production performance by electrolyzed water, and B is a graph showing the hydrazine hydrate oxidation performance. As can be seen, the synthesized material was at 1.0MKOH and 1.0M KOH +0.3M N2H4In the range of 10mA/cm in current density2The potential at this time was-0.033V and-0.025V, respectively.
Example 3
The procedure is as in example 1, except that the molar ratio of ruthenium trichloride to melamine phosphate is 1: 10.
FIG. 8 is a diagram showing the morphology and phase of the target product obtained in example 3, wherein A is a transmission electron micrograph of the target product obtained in example 3, and B is an XRD (X-ray diffraction) of the target product obtained in example 3. The figure shows that the synthesized material is a loose porous structure formed by loading ruthenium phosphide nano-particles on the surface of a carbon micron sheet and the carbon micron sheet.
FIG. 9 is a graph showing the electrocatalytic hydrogen evolution and hydrazine hydrate oxidation performance of the target product obtained in example 3, wherein A is a graph showing the hydrogen production performance by electrolyzed water, and B is a graph showing the hydrazine hydrate oxidation performance. As can be seen, the synthesized material was at 1.0M KOH and 1.0M KOH +0.3M N2H4In the range of 10mA/cm in current density2The potential at that time was-0.026V and-0.052V, respectively.
Example 4
The procedure is as in example 1, except that the molar ratio of ruthenium trichloride to melamine phosphate is 1: 20.
FIG. 10 is a diagram showing the morphology and phase of the target product obtained in example 4, wherein A is a transmission electron micrograph of the target product obtained in example 4, and B is an XRD (X-ray diffraction) of the target product obtained in example 4. The figure shows that the synthesized material is a loose porous structure formed by loading ruthenium phosphide nano-particles on the surface of a carbon micron sheet and the carbon micron sheet.
FIG. 11 is a graph showing the electrocatalytic hydrogen evolution and hydrazine hydrate oxidation performance of the target product obtained in example 4, wherein A is a graph showing the hydrogen production performance by electrolyzed water, and B is a graph showing the hydrazine hydrate oxidation performance. As can be seen, the synthesized material was at 1.0M KOH and 1.0M KOH +0.3M N2H4In the range of 10mA/cm in current density2The potential at this time was-0.034V and-0.045V, respectively.
Example 5
The preparation method was the same as example 1 except that the atmosphere was changed to Ar gas.
FIG. 12 is a diagram showing the morphology and phase of the target product obtained in example 5, wherein A is a transmission electron micrograph of the target product obtained in example 5, and B is an XRD (X-ray diffraction) of the target product obtained in example 5. The figure shows that the synthesized material is a loose porous structure formed by loading ruthenium phosphide nano-particles on the surface of a carbon micron sheet and the carbon micron sheet.
FIG. 13 is a graph showing the electrocatalytic hydrogen evolution and hydrazine hydrate oxidation performance of the target product obtained in example 5, wherein A is a graph showing the hydrogen production performance by electrolyzed water, and B is a graph showing the hydrazine hydrate oxidation performance. As can be seen, the synthesized material was at 1.0M KOH and 1.0M KOH +0.3M N2H4In the range of 10mA/cm in current density2The potential at this time was-0.030V and-0.067V, respectively.
Example 6
The preparation method is the same as that of example 1, except that the centrifugation process is changed into the stirring-drying process.
FIG. 14 is a diagram showing the morphology and phase of the target product obtained in example 6, wherein A is a transmission electron micrograph of the target product obtained in example 6, and B is an XRD (X-ray diffraction) of the target product obtained in example 6. The figure shows that the synthesized material is a loose porous structure formed by loading ruthenium phosphide nano-particles on the surface of a carbon micron sheet and the carbon micron sheet, and the particle size of the ruthenium phosphide nano-particles is about 20 nm.
FIG. 15 is a graph showing the electrocatalytic hydrogen evolution and hydrazine hydrate oxidation performance of the target product obtained in example 6A is a diagram of hydrogen production performance by electrolyzing water, and B is a diagram of oxidation performance of hydrazine hydrate. As can be seen, the synthesized material was at 1.0M KOH and 1.0M KOH +0.3M N2H4In the range of 10mA/cm in current density2The potential at this time was-0.047V and-0.070V, respectively.
Example 7
The preparation method was the same as in example 1 except that the heat treatment temperature was changed to 900 ℃.
FIG. 16 is a diagram showing the morphology and phase of the target product obtained in example 7, wherein A is a transmission electron micrograph of the target product obtained in example 7, and B is an XRD (X-ray diffraction) of the target product obtained in example 7. The figure shows that the synthesized material is a loose porous structure formed by loading ruthenium phosphide nano-particles on the surface of a carbon micron sheet and the carbon micron sheet.
FIG. 17 is a graph showing the electrocatalytic hydrogen evolution and hydrazine hydrate oxidation performance of the target product obtained in example 7, wherein A is a graph showing the hydrogen production performance by electrolyzed water, and B is a graph showing the hydrazine hydrate oxidation performance. As can be seen, the synthesized material was at 1.0M KOH and 1.0M KOH +0.3M N2H4In the range of 10mA/cm in current density2The potential at this time was-0.036V and-0.070V, respectively.
Example 8
The preparation was carried out in the same manner as in example 1 except that the heat treatment time was changed to 4 hours.
FIG. 18 is a diagram showing the morphology and phase of the target product obtained in example 8, wherein A is a transmission electron micrograph of the target product obtained in example 8, and B is an XRD (X-ray diffraction) of the target product obtained in example 8. The figure shows that the synthesized material is a loose porous structure formed by loading ruthenium phosphide nano-particles on the surface of a carbon micron sheet and the carbon micron sheet.
Example 9
The preparation was carried out in the same manner as in example 1 except that the temperature increase rate was changed to 5 ℃ per minute.
FIG. 19 is a diagram showing the morphology and phase of the target product obtained in example 9, wherein A is a transmission electron micrograph of the target product obtained in example 9, and B is an XRD (X-ray diffraction) pattern of the target product obtained in example 9. The figure shows that the synthesized material is a loose porous structure formed by loading ruthenium phosphide nano-particles on the surface of a carbon micron sheet and the carbon micron sheet.
Example 10
The preparation was carried out in the same manner as in example 1 except that the temperature increase rate was changed to 10 ℃ per minute.
FIG. 20 is a diagram showing the morphology and phase of the target product obtained in example 10, wherein A is a transmission electron micrograph of the target product obtained in example 10, and B is an XRD (X-ray diffraction) pattern of the target product obtained in example 10. The figure shows that the synthesized material is a loose porous structure formed by loading ruthenium phosphide nano-particles on the surface of a carbon micron sheet and the carbon micron sheet.
Example 11
The preparation was carried out in the same manner as in example 1 except that the temperature increase rate was changed to 20 ℃ per minute.
FIG. 21 is a chart of the morphology and phase of the target product obtained in example 11, wherein A is a TEM image of the target product obtained in example 11, and B is an XRD image of the target product obtained in example 11. The figure shows that the synthesized material is a loose porous structure formed by loading ruthenium phosphide nano-particles on the surface of a carbon micron sheet and the carbon micron sheet.
Example 12
The procedure is as in example 1 except that the organophosphorus source is replaced by azamethiphos.
FIG. 22 is a chart of the morphology and phase of the target product obtained in example 12, wherein A is a TEM image of the target product obtained in example 12, and B is an XRD image of the target product obtained in example 12. The synthesized material is a micro-nano structure formed by highly dispersing nano particles with the particle size of about 5nm in carbon, the pores are small, and the main component of the nano particles is ruthenium phosphide.
Example 13
The procedure was as in example 1 except that the organophosphorus source was changed to guanidine phosphate.
FIG. 23 is a chart of the morphology and phase of the target product obtained in example 13, wherein A is a TEM image of the target product obtained in example 13, and B is an XRD image of the target product obtained in example 13. The synthesized material is a nano-sheet structure formed by aggregating nano-particles with the particle size of about 20nm, and the main component is ruthenium phosphide.
FIG. 24 is a graph showing the electrocatalytic hydrogen evolution and hydrazine hydrate oxidation performances of the objective product obtained in example 13, wherein A is a graph showing the electrolyzed water hydrogen production performance,b is a hydrazine hydrate oxidation performance diagram. As can be seen, the synthesized material was at 1.0M KOH and 1.0M KOH +0.3M N2H4In the range of 10mA/cm in current density2The potential at this time was-0.033V and-0.074V, respectively.
Example 14
The preparation method was the same as in example 1 except that the organophosphorus source was changed to guanylurea phosphate and the stirring and centrifuging process was directly changed to a physical mixing process.
FIG. 25 is a chart of the morphology and phase of the target product obtained in example 14, wherein A is a TEM image of the target product obtained in example 14, and B is an XRD image of the target product obtained in example 14. The synthesized material is a micro-nano structure formed by embedding nano particles into carbon, the structure is compact, the pores are small, and the main component of the nano particles is ruthenium phosphide.
FIG. 26 is a graph showing the electrocatalytic hydrogen evolution and hydrazine hydrate oxidation performance of the target product obtained in example 14, wherein A is a graph showing the hydrogen production performance by electrolyzed water, and B is a graph showing the hydrazine hydrate oxidation performance. It can be seen that the synthesized material is at 1.0M KOH and 1.0M KOH +0.3M N2H4In the range of 10mA/cm in current density2The potential at this time was-0.023V and-0.065V, respectively.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (4)
1. A preparation method of a ruthenium phosphide-loaded carbon micron sheet bifunctional electrocatalyst is characterized by comprising the following steps of:
dispersing ruthenium trichloride and an organic phosphorus source compound in ethanol, stirring, centrifuging and drying to obtain a precursor;
heating the precursor to 850-900 ℃ at a heating rate of 2-20 ℃/min under a protective atmosphere, and calcining for 2-4 h to obtain the ruthenium phosphide-loaded carbon micron sheet dual-functional electrocatalyst;
the organic phosphorus source compound is selected from one or more of melamine phosphate, guanidine phosphate and guanylurea phosphate;
the bifunctional electrocatalyst is a composite structure of ruthenium phosphide nanoparticles and carbon nanosheets;
the particle size of the ruthenium phosphide nano-particles is 5-20 nm.
2. The preparation method according to claim 1, wherein the molar ratio of the ruthenium trichloride to the organophosphorus source compound is 1:5 to 1: 20.
3. The method for preparing according to claim 1, wherein the centrifugation is in particular: centrifuge at 8000rpm for 2 min.
4. The method according to claim 1, wherein the protective atmosphere is argon-hydrogen mixture gas or argon gas.
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