CN112108146B - Phase-transformed ruthenium oxide, preparation method thereof and application thereof in hydrogen production by seawater electrolysis - Google Patents
Phase-transformed ruthenium oxide, preparation method thereof and application thereof in hydrogen production by seawater electrolysis Download PDFInfo
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- CN112108146B CN112108146B CN202011048677.4A CN202011048677A CN112108146B CN 112108146 B CN112108146 B CN 112108146B CN 202011048677 A CN202011048677 A CN 202011048677A CN 112108146 B CN112108146 B CN 112108146B
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- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229910001925 ruthenium oxide Inorganic materials 0.000 title claims abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 19
- 239000001257 hydrogen Substances 0.000 title claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title claims description 7
- 239000013535 sea water Substances 0.000 title abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 8
- 238000000634 powder X-ray diffraction Methods 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000002441 X-ray diffraction Methods 0.000 claims description 5
- 125000003158 alcohol group Chemical group 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 2
- 239000011259 mixed solution Substances 0.000 claims 2
- 238000003756 stirring Methods 0.000 claims 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims 2
- 239000000843 powder Substances 0.000 claims 1
- 238000004729 solvothermal method Methods 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- -1 Na + Chemical class 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000004832 voltammetry Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Classifications
-
- 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
-
- B01J35/33—
-
- B01J35/50—
-
- 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 method for preparing phase-converted ruthenium oxide, which is characterized in that the phase-converted ruthenium oxide is obtained after the treatment by a solvothermal method, and an X-ray powder diffraction pattern deviates a plurality of diffraction peaks or generates new diffraction peaks at a small angle relative to an XRD standard pattern of ruthenium dioxide. The invention adopts a solvothermal method which is easy to realize industrially to treat ruthenium dioxide to obtain phase-converted ruthenium oxide, can greatly improve the water electrolysis performance of the material and the hydrogen production performance of the electrolytic seawater, and has extremely strong practical significance.
Description
Technical Field
The invention belongs to the field of inorganic nano catalytic material manufacturing, and particularly relates to an improved method of ruthenium dioxide and application of the improved method in water electrolysis and seawater electrolysis to hydrogen production.
Background
Seawater is liquid water with the most extensive distribution and the most abundant reserves on the earth, and hydrogen can be produced by electrolyzing seawaterRealize green efficient and sustainable preparation of hydrogen, but seawater is generally neutral and slightly alkaline in pH, complex in composition and contains a plurality of metal cations (such as Na + 、K + 、Ca 2+ And Mg (magnesium) 2+ Etc.) and anions (e.g. Cl) - 、SO 4 2- 、Br - And HCO 3 - Etc.), so that the electrocatalyst faces the problems of low catalytic activity and poor stability at the same time. Noble metal catalysts such as commercial Pt/C and commercial RuO 2 Commercial IrO 2 Compared with a non-noble metal catalyst, the catalyst has better catalytic activity and relatively higher stability in electrolyte with a wide pH range, and is used as a reference comparison catalyst for evaluating the performance of electrolyzed water. Ruthenium (Ru) is the cheapest noble metal of the Pt group, whose valence can vary from-II to +VIII, yielding many compounds with unique properties. Wherein RuO is as follows 2 Becomes an electrooxygen-evolving catalyst widely used at present, and relates to RuO 2 The application of electrocatalytic hydrogen evolution has also been reported for a long time, and has better catalytic activity, but the problem of catalytic stability is always present and is difficult to solve. For RuO 2 Problems of improving the catalytic activity and stability thereof, researchers have made extensive research and study, such as preparing RuO of different sizes, morphologies, crystallinity and exposed crystal planes 2 The catalytic activity and stability of the material are regulated and controlled by doping other metals or forming a multi-metal compound and a multi-metal solid solution. However, numerous strategies have complicated methods and are difficult to simultaneously improve the catalytic performance of the electrolytic seawater hydrogen evolution and anodic oxidation reaction of the material, so that the development of a catalyst with high catalytic activity and high stability is a core problem facing the field of electrolytic seawater, thereby improving RuO 2 The simple method of producing hydrogen from electrolyzed seawater remains a challenge.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a post-treatment method of ruthenium dioxide, which can effectively improve the hydrogen production performance of ruthenium dioxide electrolyzed water and electrolyzed seawater by changing the phase structure of the whole material through treatment.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a phase-transformed ruthenium oxide whose X-ray powder diffraction pattern is slightly shifted or generates a new diffraction peak with respect to a plurality of diffraction peaks in an XRD standard pattern of ruthenium dioxide, wherein the position of the corresponding peak of the (110) crystal face is shifted from 27.5 to 28.5 ° to the left by 1.5 to 2 °, while the corresponding diffraction peak of the (101) crystal face disappears at 34.5 to 35.5 ° and generates 3 new relatively weak peaks between 35.4 to 37.4 ° at a higher angle, the intensity of the diffraction peak of the (211) crystal face at 53.8 to 54.8 ° is not significantly weakened but the peak width becomes large, and a new diffraction peak is generated at the left shift of 1.5 to 2.5 °, and the vicinity of other diffraction peaks with weaker intensities is accompanied by a similar change.
The preparation method of the phase-converted ruthenium oxide comprises the following steps:
(1) Adding ruthenium dioxide into a solvent, and performing ultrasonic treatment to obtain a black solution; wherein the solvent is alcohol or alcohol solution of alkali;
(2) And (3) standing the solution obtained in the step (1) at a certain temperature and preserving heat for a certain time to obtain the phase-converted ruthenium oxide.
In the scheme, the alkali in the step (1) is one or a mixture of several alkaline hydroxides such as sodium hydroxide, potassium hydroxide and the like according to any proportion.
In the above scheme, the concentration of the alkali in the alkali alcoholic solution is in the range of 0 to 3mol/L. The alkali can accelerate the phase transformation process, and the phase transformation can be completed by prolonging the reaction time without adding alkali.
In the scheme, the dispersion concentration of the ruthenium dioxide added in the step (2) in the solvent is in the range of 0.05-200 mg/mL. The ruthenium dioxide is rutile type ruthenium dioxide, can be commercial ruthenium dioxide, can be synthesized according to literature, and has the size of 10 nm-10 μm, preferably nano-scale particles, and the size is distributed between 50 nm-200 nm.
In the above scheme, the alcohol in the step (1) may be one or more of low-carbon organic alcohols such as methanol, ethanol, ethylene glycol and glycerin.
In the scheme, the temperature in the step (2) is 100-200 ℃, and the heat preservation time is 2-48 h.
In the above preparation method, the phase transition of ruthenium dioxide is caused by solvothermal treatment, and the phase structure is reflected in that a plurality of diffraction peaks in an X-ray powder diffraction pattern are shifted at a small angle or new diffraction peaks are generated. The ruthenium oxide with phase transition prepared by the method can be used as a catalyst in the hydrogen production of electrolyzed water and electrolyzed seawater.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
firstly, the invention adopts a solvothermal method which is easy to realize in industry to treat ruthenium dioxide particles to obtain phase-converted ruthenium oxide, and can greatly improve the water electrolysis performance of the material and the hydrogen production performance of the electrolytic seawater. Secondly, the method for post-treating ruthenium dioxide provided by the invention is simple and feasible, stable and safe in reaction, low in cost, capable of large-scale synthesis and suitable for industrial production.
Drawings
FIG. 1 (a) is an SEM image of the phase-converted ruthenium oxide obtained after 8 hours of reaction of ruthenium dioxide in example 1 of the present invention with ethylene glycol and sodium hydroxide solvent at 140 ℃, (b) is an SEM image of commercial ruthenium dioxide;
FIG. 2 is an XRD pattern of ruthenium dioxide in example 1 of the present invention after a reaction of ethylene glycol and sodium hydroxide in a solvent at 140℃for 8 hours;
FIGS. 3 (a) and (b) are linear voltammetry curves of electrohydrogen and electrooxygen in 1mol/L KOH electrolyte, respectively, (c) and (d) are linear voltammetry curves of electrohydrogen and current density of 10mA/cm, respectively, simulating seawater 2 Stability test below. RuO (Ruo) 2 -140 is ruthenium oxide phase-converted obtained after reaction of ruthenium dioxide in example 1 with ethylene glycol and sodium hydroxide solvent at 140 ℃ for 8 hours; in contrast, the commercial RuO 2 For commercial ruthenium dioxide, commercial Pt/C is commercial Pt/C;
FIG. 4 is an SEM image of ruthenium dioxide of example 2 of the present invention after reaction of ethylene glycol with sodium hydroxide at 160℃for 8 hours in solvent;
FIG. 5 is an XRD pattern of ruthenium dioxide in example 2 of the present invention after a reaction of ethylene glycol and sodium hydroxide in a solvent at 160℃for 8 hours;
FIG. 6 is an SEM image of the phase-converted ruthenium oxide obtained after 24 hours of reaction of ruthenium dioxide in example 3 of the present invention at 140℃in ethylene glycol solvent;
FIG. 7 is an XRD pattern of ruthenium dioxide in example 3 of the present invention after 24 hours of reaction at 140℃in a glycol solvent;
FIG. 8 is an XRD pattern of ruthenium dioxide in example 4 of the present invention after 20 hours of reaction at 160℃in a glycerin solvothermal.
Detailed Description
For a better understanding of the present invention, the following examples are further illustrated, but are not limited to the following examples.
In the examples described below, the starting ruthenium dioxide used is commercially available ruthenium dioxide in the rutile form, the size being predominantly distributed between 50nm and 200 nm.
Example 1
A method for preparing phase-transformed ruthenium oxide, comprising the following steps:
(1) Mixing 0.6g of sodium hydroxide with 15mL of ethylene glycol, and dissolving to obtain a colorless transparent solution;
(2) Adding 100mg of commercial ruthenium dioxide to the solution in (1), and performing ultrasonic treatment to obtain a black solution;
(3) Placing the solution obtained in the step (2) in an oil bath pot at 140 ℃ for 8 hours; the resulting product was washed by centrifugation with water and the sample was freeze-dried.
The SEM of phase-converted ruthenium oxide prepared in this example is shown in FIG. 1, which shows a morphology that is more roughened than commercial ruthenium dioxide.
XRD of the phase-converted ruthenium oxide prepared in this example was shown in FIG. 2, with respect to the commercial ruthenium dioxide phase conversion. As can be seen from FIG. 2, the X-ray powder diffraction pattern of ruthenium oxide obtained by the phase transformation of the example was slightly shifted from the multiple diffraction peaks in the XRD standard pattern of ruthenium dioxide, wherein the position of the corresponding peak of the (110) crystal face was shifted from 27.5 to 28.5 deg. to the left by 1.5 to 2 deg., while the corresponding diffraction peak of the (101) crystal face was disappeared at 34.5 to 35.5 deg., and 3 relatively weak new peaks were generated between 35.4 to 37.4 deg. at higher angles, the intensity of the diffraction peak of the (211) crystal face at 53.8 to 54.8 deg. was not significantly weakened but the peak width was enlarged, and a new diffraction peak was generated at the left shift of 1.5 to 2.5 deg., and similar changes were accompanied in the vicinity of the other diffraction peaks with weaker intensities, not shown.
The electrocatalytic performance test of the phase-converted ruthenium oxide prepared in this example is shown in fig. 3, and includes the following steps:
(1) Preparation of electrocatalyst ink. First, an ink was prepared with 950. Mu.l of isopropanol, 50. Mu.l of a 5wt% Nafion solution and 5mg of a catalyst. Then, the ink prepared by the catalyst was mixed with ultrasound for 30 minutes, confirming that the catalyst ink was uniformly dispersed. The ultrasonic uniform ink 10. Mu.L was dropped onto a rotary disk electrode having a diameter of 5mm twice, and naturally dried.
(2) And (5) testing the electrocatalytic hydrogen evolution and oxygen evolution performance. The experiment is carried out on an Autolab electrochemical analyzer, all electrochemical performance characterizations are completed under a three-electrode system, an Ag/AgCl electrode is used as a reference electrode, a carbon rod is used as a counter electrode, and a working electrode is a rotary disk electrode. Respectively neutralizing 1mol/L PBS buffer solution with 1mol/L KOH electrolyte to simulate seawater containing 3.5wt% NaCl (measured pH is 5.8), and introducing saturated N 2 The sweep rate is the hydrogen evolution, oxygen evolution linear voltammogram tested at 5mV/s, with the abscissa being the voltage relative to the reversible hydrogen electrode (vs. RHE) and the ordinate being the current density.
As can be seen from FIG. 3, the phase-converted ruthenium oxide obtained in example 1 (overpotential 28mV@10mA/cm 2 ) Exhibits a specific commercial Pt/C (overpotential 61mV@10mA/cm 2 ) The hydrogen evolution performance is more excellent, and compared with the commercial ruthenium oxide, the hydrogen evolution performance and the oxygen evolution performance are greatly improved. In the simulated seawater electrolyte containing 3.5wt% NaCl in 1mol/L PBS buffer solution, the electrohydrogen current density reaches 10mA/cm 2 When RuO is used 2 -140, commercial RuO 2 And commercial Pt/C overpotential of 113mV,194mV and 35mV, respectively, ruO 2 -140 vs. commercial RuO 2 The performance was greatly improved, while in stability testing, it was seen that the performance of commercial Pt/C was compared to RuO 2 The material decays very fast, comprehensively compares, ruO 2 -140 exhibits excellent activity and stability of hydrogen production by electrolysis of seawaterSex.
Example 2
A method for preparing phase-transformed ruthenium oxide, comprising the following steps:
(1) Mixing 0.6g of sodium hydroxide with 15mL of ethylene glycol, and performing ultrasonic treatment until the mixture is dissolved to obtain colorless transparent liquid;
(2) Adding 50mg of commercial ruthenium dioxide to the solution of (1), and performing ultrasonic treatment to obtain a black solution;
(3) Placing the solution obtained in the step (2) into an oil bath pot at 160 ℃ for reaction for 8 hours; the obtained product is centrifugally separated and washed by water to obtain the ruthenium oxide with phase transition.
The SEM of phase-converted ruthenium oxide prepared in this example is shown in FIG. 4, which shows a morphology that is comparable to that of commercial ruthenium dioxide.
XRD of the phase-converted ruthenium oxide prepared in this example was as shown in FIG. 5, and the diffraction peak thereof was changed as in example 1.
Example 3
A method for preparing phase-transformed ruthenium oxide, comprising the following steps:
(1) 50mg of commercial ruthenium dioxide was mixed with 15mL of ethylene glycol solution and sonicated to obtain a black solution;
(2) Placing the solution obtained in the step (1) into an oil bath pot at 140 ℃ for reaction for 24 hours; the obtained product is centrifugally separated and washed by water to obtain the ruthenium oxide with phase transition.
The SEM of phase-converted ruthenium oxide prepared in this example is shown in FIG. 6, which shows a morphology that is more roughened than commercial ruthenium dioxide.
The XRD of the phase-converted ruthenium oxide prepared in this example is shown in FIG. 7, and the XRD diffraction peak thereof is shifted by a partial degree of phase conversion, but at the same time, a part of the diffraction peak of the original ruthenium dioxide is also maintained. Although the reaction was described as being carried out without adding a base, the phase transition rate was slow, it is expected that the phase transition could be completed by increasing the temperature or prolonging the heating time.
Example 4
A method for preparing phase-transformed ruthenium oxide, comprising the following steps:
(1) 50mg of commercial ruthenium dioxide was mixed with 15mL of glycerol and sonicated to obtain a black solution;
(2) Placing the solution obtained in the step (1) in an oil bath pot at 160 ℃ and preserving heat for 20 hours; the obtained product was washed by centrifugation with water to obtain phase-converted ruthenium oxide.
As shown in FIG. 8, XRD of the phase-converted ruthenium oxide prepared in this example, since no alkali was added to the alcohol solution, the X-ray powder diffraction peak was substantially similar to that of example 1 by increasing the temperature and prolonging the heating time in order to phase-convert the ruthenium dioxide, and it was revealed that the phase-converted ruthenium oxide was prepared.
It is apparent that the above examples are only examples given for clarity of illustration and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it intended to be exhaustive of all embodiments, and thus all obvious variations or modifications that come within the scope of the invention are desired.
Claims (5)
1. A phase-converted ruthenium oxide, characterized by: the XRD pattern of the method is relative to the XRD standard pattern of ruthenium dioxide, and a plurality of diffraction peaks deviate at small angles or generate new diffraction peaks;
wherein, the position of the peak corresponding to the (110) crystal face deviates from 27.5-28.5 degrees to the left by 1.5-2 degrees, the diffraction peak corresponding to the (101) crystal face disappears at 34.5-35.5 degrees, and 3 weaker new peaks are generated at the angle of 35.4-37.4 degrees; (211) The peak width of diffraction peak of crystal face at 53.8-54.8 deg. becomes larger, and a new diffraction peak is generated at the position of left offset 1.5-2.5 deg.;
the preparation method of the phase-converted ruthenium oxide comprises the following steps:
(1) Adding ruthenium dioxide into a solvent, and performing ultrasonic dispersion or stirring and dispersing uniformly; wherein the solvent is an alcohol; or the solvent is a mixed solution of alcohol and alkali; the concentration of hydroxyl in the alkali alcohol solution ranges from 0 to 3mol/L and is not 0; the dispersion concentration range of ruthenium dioxide in the solvent is 0.05-200 mg/mL;
(2) And (3) standing the solution obtained in the step (1) at 100-200 ℃ and preserving heat for 2-48 and h to obtain the phase-converted ruthenium oxide, wherein the phase structure is reflected by small-angle deviation of a plurality of diffraction peaks in an X-ray powder diffraction pattern or generation of new diffraction peaks.
2. The method for preparing phase-transformed ruthenium oxide according to claim 1, wherein: the method comprises the following steps:
(1) Adding ruthenium dioxide into a solvent, and performing ultrasonic dispersion or stirring and dispersing uniformly; wherein the solvent is an alcohol; or the solvent is a mixed solution of alcohol and alkali; the concentration of hydroxyl in the alkali alcohol solution ranges from 0 to 3mol/L and is not 0; the dispersion concentration range of ruthenium dioxide in the solvent is 0.05-200 mg/mL;
(2) And (3) standing the solution obtained in the step (1) at 100-200 ℃ and preserving heat for 2-48 and h to obtain the phase-converted ruthenium oxide, wherein the phase structure is reflected by small-angle deviation of a plurality of diffraction peaks in an X-ray powder diffraction pattern or generation of new diffraction peaks.
3. The method for producing phase-transformed ruthenium oxide according to claim 2, wherein: the ruthenium dioxide in the step (1) is rutile type powder.
4. The method for producing phase-transformed ruthenium oxide according to claim 2, wherein: the alcohol in the step (1) is at least one of methanol, ethanol, glycol and glycerol; the alkali is at least one of soluble inorganic alkali.
5. Use of the phase-transformed ruthenium oxide according to claim 1 as electrocatalytic material for hydrogen production by electrolysis of water.
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| CN202011048677.4A CN112108146B (en) | 2020-09-29 | 2020-09-29 | Phase-transformed ruthenium oxide, preparation method thereof and application thereof in hydrogen production by seawater electrolysis |
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| CN202011048677.4A CN112108146B (en) | 2020-09-29 | 2020-09-29 | Phase-transformed ruthenium oxide, preparation method thereof and application thereof in hydrogen production by seawater electrolysis |
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| Publication Number | Publication Date |
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