CN113443610A - Ruthenium selenide nanosphere electrocatalyst and preparation method and application thereof - Google Patents

Ruthenium selenide nanosphere electrocatalyst and preparation method and application thereof Download PDF

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CN113443610A
CN113443610A CN202110779961.7A CN202110779961A CN113443610A CN 113443610 A CN113443610 A CN 113443610A CN 202110779961 A CN202110779961 A CN 202110779961A CN 113443610 A CN113443610 A CN 113443610A
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nanosphere
ruse
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CN113443610B (en
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马江权
詹伟
李楠
李正萍
郭志敏
强成宏
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Changzhou University
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    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/007—Tellurides or selenides of metals
    • 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
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    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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    • C01—INORGANIC CHEMISTRY
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    • C01P2004/00—Particle morphology
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/30—Particle morphology extending in three dimensions
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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Abstract

The invention belongs to the field of preparation and application of electrocatalysts, and particularly relates to a ruthenium selenide nanosphere electrocatalyst, and a preparation method and application thereof2The nanosphere electrocatalyst has excellent hydrogen evolution performance in KOH and performance close to that of a noble metal Pt/C catalyst. The invention provides a method for preparing RuSe by adopting a microwave and calcination two-step method2The nanosphere electrocatalyst has the advantages of short synthesis time, simple operation, greenness and no pollution, and the catalyst shows excellent hydrogen evolution activity and good stability in the electrocatalyst.

Description

Ruthenium selenide nanosphere electrocatalyst and preparation method and application thereof
Technical Field
The invention belongs to the field of preparation and application of electrocatalysts, and particularly relates to a ruthenium selenide nanosphere electrocatalyst as well as a preparation method and application thereof.
Background
Hydrogen fuel is renewable, free of greenhouse gas emissions and energy dense in all fuelsThe most advanced are considered promising candidate fuels to address the global environmental and energy crisis. Currently, the widely used method for producing hydrogen fuel is steam reforming of fossil fuel, but this process generates emissions of carbon dioxide and air pollutants. Hydrogen production by electrochemical cracking of water has received more and more attention in recent years as an advanced clean energy conversion technology. The key to this technique is the two half-reactions of the cathodic Hydrogen Evolution Reaction (HER) and the anodic Oxygen Evolution Reaction (OER), which produce H separately2And O2A gas.
In alkaline electrolytes, the HER process is not only dependent on H2The adsorption kinetics of O also depends on H2The dissociation rate of O. Although Ru is a noble metal catalyst, the price of Ru is far lower than that of Pt, and Ru has good water dissociation energy and hydrogen bond strength almost equivalent to that of Pt. However, Ru metal exhibits high affinity for oxygen, resulting in too strong adsorption of oxygen-containing species (OH;) and too slow release of active sites in the subsequent hydrogen evolution process, thereby hindering the overall hydrogen evolution process.
Disclosure of Invention
The invention aims to provide RuSe2The nanosphere electrocatalyst and the preparation method thereof are applied to the preparation of hydrogen by decomposing water under the alkaline condition, and have high catalytic activity and good stability.
The technical scheme of the invention is as follows: the invention provides RuSe2The preparation method of the nanosphere electrocatalyst comprises the following steps: adding RuCl3The aqueous solution and selenium source were dispersed in ethylene glycol and stirred well. Placing the dispersion liquid in a microwave reactor for microwave reaction, centrifugally washing and vacuum drying the obtained precipitate, and further calcining in a tubular furnace to obtain crystalline RuSe2Nanosphere electrocatalysts.
The specific process comprises the following steps:
(1) adding a certain amount of Se powder or H2SeO3Dissolving as selenium source in ethylene glycol, and stirring thoroughly until it is completely dispersed. Wherein, Se powder or H2SeO3The molar ratio of the compound to the ethylene glycol is as follows: 1: 1000-1: 5000.
Preferably, the method comprises the following steps: 50ml of ethylene glycol is weighed by a measuring cylinder and poured into a beaker, 0.0311g of Se powder is added, and the mixture is fully stirred for 1 hour.
(2) Adding a certain amount of RuCl3Slowly adding the mixture into the dispersion liquid obtained in the step (1), stirring and carrying out ultrasonic treatment until the mixture is uniformly dispersed, and adjusting the pH value of the solution to be alkaline by using KOH. Wherein RuCl is added3With Se powder or H2SeO3The molar ratio of (A) to (B) is: 1: 1-1: 3, and adjusting the pH range of the solution to be: 6 to 10.
Preferably, the method comprises the following steps: 0.0181g of RuCl was weighed3Slowly adding into a beaker filled with the dispersion liquid in the step (1), stirring and dispersing for 1h, ultrasonically dispersing for 1h uniformly, and adjusting to be alkaline by using a KOH solution with the concentration of 0.1mol/L to ensure that the pH value of the solution is 8.
(3) And (3) reacting the dispersion liquid obtained in the step (2) in a rapid microwave reactor at a certain temperature for a certain time, cooling the reacted solution to room temperature, centrifugally washing and drying in vacuum.
Wherein, the power of the rapid microwave reactor is as follows: 600W-1000W, and the reaction time in the rapid microwave reactor is as follows: 2min to 6 min.
Preferably, the method comprises the following steps: placing the beaker filled with the dispersion liquid in the step (2) in a microwave reactor, setting the power of the microwave reactor to be 800W, reacting for 3 minutes, cooling to room temperature after the reaction is finished, centrifugally washing the suspension containing the product for 5-6 times to remove residual glycol, placing the product in a vacuum drying oven at 60 ℃ overnight to obtain a product RuSe2And (3) precursor.
(4) The product obtained in the step (3) is RuSe2Placing the precursor in N2Calcining in an atmosphere tube furnace at different times and temperatures to obtain the final product of crystalline RuSe2Nanosphere electrocatalysts.
The calcination temperature in the tube furnace was: the calcining time is between 200 and 600 ℃ as follows: 1 to 4 hours.
Preferably, the method comprises the following steps: the product RuSe in the step (3)2Placing the precursor in a crucible, and placing the crucible in N2Setting the controlled heating rate at 5 ℃/min, the calcining temperature at 500 ℃ and the calcining time at 2h in an atmosphere tube furnace, and obtaining the final product of crystal RuSe2Nanospheres.
The invention selects proper selenium source, control Se powder and RuCl3The ratio of (A) and the microwave reaction time, and the like, by using a microwave method to synthesize the RuSe2Precursor, and then different calcining temperatures and times are changed to prepare the crystal RuSe2Nanospheres. By controlling the calcination temperature and time, RuSe with higher crystallization degree and regular appearance can be obtained2The composite electro-catalyst has high catalytic activity and good stability in the electro-catalytic hydrogen evolution reaction due to the nano-sphere electro-catalyst.
The invention also provides RuSe2The nanosphere electrocatalyst is used as a working electrode in the application of preparing hydrogen by electrolyzing water under an alkaline condition.
Electrocatalyst RuSe prepared by microwave and calcination two-step method2The method for testing the performance of the hydrogen evolution by applying the nanospheres to the electrocatalysis uses a three-electrode system, and a working electrode is loaded with RuSe2The glassy carbon electrode is a graphite rod electrode as a counter electrode, an Hg/HgO electrode as a reference electrode and a 1mol/L KOH solution as electrolyte.
The invention has the technical effects that:
(1) the invention provides a method for preparing crystal RuSe by using a microwave and calcination two-step method2Compared with the traditional hydrothermal method and other methods, the nanosphere has the characteristics of novel synthesis method, simple conditions, easy operation, high speed, high efficiency, energy conservation, environmental protection, easy industrial production and the like;
(2) the invention provides a method for preparing RuSe by using a microwave method2The precursor has good crystallinity and regular morphology by controlling the calcination temperature and time, increases the electrochemical active surface area, and has high activity and good stability for the electrocatalytic hydrogen evolution reaction;
(3) the invention provides a method for preparing crystal RuSe by using a microwave and calcination two-step method2The nanosphere has high catalytic hydrogen evolution activity and good stability in alkaline electrolyte, and is used for preparing hydrogen by electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L and using calcined crystal RuSe2The nanosphere is used as a working electrode, and the current density is-10 mA/cm2When the reaction is carried out, the overpotential is only 29mV, which is shown in the hydrogen evolution reaction of the electrolyzed waterExcellent catalytic performance and stability.
Drawings
FIG. 1 shows RuSe crystals obtained in example 1 of the present invention2SEM image of nanospheres.
FIG. 2 shows RuSe crystals obtained in example 2 of the present invention2SEM image of nanospheres.
FIG. 3 shows RuSe crystals obtained in example 3 of the present invention2SEM image of nanospheres.
FIG. 4 shows RuSe crystals obtained in example 4 of the present invention2SEM image of nanospheres.
FIG. 5 shows RuSe crystals obtained in example 5 of the present invention2SEM image of nanospheres.
FIG. 6 shows RuSe crystals obtained in comparative example 2 of the present invention2SEM image of nanospheres.
FIG. 7 shows RuSe crystals obtained in examples 1 to 5 of the present invention2XRD pattern of nanospheres.
FIG. 8 shows RuSe crystals obtained in examples 1 to 5 of the present invention2Polarization profile of nanospheres in 1.0M KOH solution to electrolyze water HER.
FIG. 9 shows RuSe crystals obtained in examples 1 to 5 of the present invention2Tafel plot of nanospheres on HER in 1.0M KOH solution.
FIG. 10 shows RuSe crystals obtained in example 1 of the present invention2Polarization curve obtained before and after 1000 cycles of cyclic voltammetry scan test of nanosphere (built-in graph is crystal RuSe obtained in example2Current time curve of nanosphere electrolyzing water at overpotential 29mV for 17 hours).
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the following examples.
Example 1
Preparation of Se powder Dispersion
50ml of ethylene glycol is weighed by a measuring cylinder and poured into a beaker, 0.0311g of Se powder is added, and the mixture is fully stirred for 1 hour.
Preparation of 2.1mol/L KOH solution
50mL of ultrapure water and 5.61g of potassium hydroxide were measured, dissolved and stirred in ultrapure water, cooled, and then fixed to a volume in a 100mL volumetric flask.
Se powder dispersion and RuCl3Preparation of the Mixed solution
Accurately weighing 0.0181g of RuCl3Slowly adding into a beaker filled with Se dispersion liquid, stirring and dispersing for 1h, ultrasonically dispersing for 1h uniformly, and adjusting to be alkaline by using KOH solution with the concentration of 0.1mol/L to ensure that the pH value of the solution is 8.
4.RuSe2Preparation of nanospheres
(1) Placing the beaker filled with the dispersion liquid in a microwave reactor, setting the power of the microwave reactor to be 800W, reacting for 3min, cooling to room temperature after the reaction is finished, centrifugally washing the suspension containing the product for 5 times to remove the residual glycol, placing the product in a vacuum drying oven at 60 ℃ overnight to obtain a product RuSe2And (3) precursor.
(2) Mixing RuSe2Placing the precursor in a crucible, and placing the crucible in N2Setting the controlled heating rate at 5 ℃/min, the calcining temperature at 500 ℃ and the calcining time at 2h in an atmosphere tube furnace, and obtaining the final product of crystal RuSe2Nanospheres.
Crystalline RuSe prepared in example 12The SEM picture is shown in figure 1, the XRD picture is shown in figure 7, and the prepared RuSe can be seen from the XRD and the scanning electron microscope picture2The characteristic peak of the nanometer sphere XRD is sharp and obvious, and is similar to the standard card RuSe2Completely conforms to the shape of a uniform regular sphere, and the prepared crystal RuSe2The nanosphere has good crystallinity and regular morphology.
Example 2
Compared with example 1, the difference is that: in RuSe2The calcining temperature is set to 200 ℃ in the step (2) of preparing the nanospheres, and other preparation methods are the same as those of the example 1. The prepared RuSe can be seen from XRD and scanning electron microscope images2With RuSe2The precursor has similar characteristic peaks, mainly characteristic peaks of Se powder, but the morphology of the product is not regular enough.
Example 3
Compared with example 1, the difference is that: in RuSe2Preparation of nanospheresThe calcination temperature in step (2) was set to 300 ℃, and the other preparation methods were the same as in example 1. The prepared RuSe can be seen from XRD and scanning electron microscope images2With RuSe2Compared with the precursor, the characteristic peak is obviously changed, and compared with RuSe2The standard card characteristic peak completely corresponds to the standard card characteristic peak, but the product crystallinity is still not high, and the appearance is regular spheroidal.
Example 4
Compared with example 1, the difference is that: in RuSe2The calcining temperature is set to 400 ℃ in the step (2) of preparing the nanospheres, and other preparation methods are the same as those of example 1. The prepared RuSe can be seen from XRD and scanning electron microscope images2The characteristic peak is more obvious, the crystallinity of the product is also improved, and the appearance is more uniform and regular sphere.
Example 5
Compared with example 1, the difference is that: in RuSe2The calcining temperature is set to 600 ℃ in the step (2) of preparing the nanospheres, and other preparation methods are the same as those of the example 1. The prepared RuSe can be seen from XRD and scanning electron microscope images2The characteristic peak is more sharp and obvious, the crystallinity of the product is higher, and the appearance is uniform and regular sphere.
Example 6
Compared with example 1, the difference is that: RuCl3The molar ratio of Se powder to Se powder is 1:3, and the other preparation methods are the same as example 1.
Example 7
Compared with example 1, the difference is that: RuCl3The molar ratio of Se powder to Se powder is 1:1, and the other preparation methods are the same as those of example 1.
Example 8
Compared with example 1, the difference is that: changing Se powder to 0.0508g H2SeO3The other preparation methods are the same as example 1.
Example 9
Compared with example 1, the difference is that: the molar ratio of Se powder to ethylene glycol is as follows: 1:5000, and the other preparation methods are the same as example 1.
Comparative example 1
Compared with example 1, the difference is that: deionized water was used as a reaction solvent instead of ethylene glycol, and the other preparation methods were the same as in example 1. When the ionic water is used as a reaction solvent instead of ethylene glycol, the reactant Se powder cannot be completely dispersed and dissolved, and the reaction is not sufficiently complete.
Comparative example 2
Compared with example 1, the difference is that: without RuSe being carried out2The calcination step in the step (2) of preparing nanospheres was performed in the same manner as in example 1. The prepared RuSe can be seen from XRD and scanning electron microscope images2The characteristic peak of the precursor XRD is mainly the characteristic peak of Se powder, and the product has poor crystallinity and irregular and uniform appearance.
The raw material amount ratios, reaction conditions, and electrocatalysts prepared in the above examples and comparative examples gave anodes at current densities of 10mA/cm2The overpotential of time is shown in table 1.
TABLE 1
Figure BDA0003156207390000071
Application example 1
1. Activation treatment of electrocatalyst
(1) Catalyst ink was prepared by dispersing 2mg of the catalyst and 10. mu.L of 5 wt% Nafion in a mixed solution containing 375. mu.L of ultrapure water and 125. mu.L of ethanol. After continuing the ultrasonic treatment for 20 minutes, 5. mu.L of the uniform ink was dropped on a previously polished glassy carbon electrode having a diameter of 3mm, and then naturally dried at room temperature.
(2) Using a three-electrode system, the working electrode was surface-drop coated with the crystalline RuSe of example 12The glassy carbon electrode is a graphite rod electrode as a counter electrode, an Hg/HgO electrode as a reference electrode and 1mol/L KOH as electrolyte;
(3) cyclic Voltammetry (CV) activation: the Shanghai Chenghua DH7000 electrochemical workstation is used, a CV program is adopted, the test interval is-0.8 to-1.6V vs. RHE, the sweep rate is 50mV/s, the electrode is circulated for 20 circles, and the electrode reaches a stable state.
2. Linear Sweep Voltammetry (LSV) testing
After activation, the program is switched to linear sweepA voltammetry-tracing program, the test interval is-0.8 to-1.6V vs. RHE, the sweep rate is 5mV/s, and the electro-catalyst is at-10 mA/cm in alkaline electrolyte2The overpotential was 29mV, as shown in FIG. 8.
3. Stability test
After activation, the switching program was a chronoamperometry program with a voltage setting of 29mv and a time setting of 61200 s. As shown in fig. 10, the voltage variation of the electrocatalyst is not large, demonstrating its good stability.
Application example 2
RuSe prepared in example 2 as shown in application example 12The electrocatalyst is used for preparing hydrogen by electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L, and the anode of the electrocatalyst is used for preparing hydrogen by electrocatalysis in KOH electrolyte with the current density of 10mA/cm2An electrocatalyst with an overpotential of 86 mV.
Application example 3
RuSe prepared in example 3 as shown in application example 12The electrocatalyst is used for preparing hydrogen by electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L, and the anode of the electrocatalyst is used for preparing hydrogen by electrocatalysis in KOH electrolyte with the current density of 10mA/cm2An overpotential of 68mV for the electrocatalyst.
Application example 4
RuSe prepared in example 4 as shown in application example 12The electrocatalyst is used for preparing hydrogen by electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L, and the anode of the electrocatalyst is used for preparing hydrogen by electrocatalysis in KOH electrolyte with the current density of 10mA/cm2An electrocatalyst with an overpotential of 49 mV.
Application example 5
RuSe prepared in example 5 as shown in application example 12The electrocatalyst is used for preparing hydrogen by electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L, and the anode of the electrocatalyst is used for preparing hydrogen by electrocatalysis in KOH electrolyte with the current density of 10mA/cm2An electrocatalyst with an overpotential of 39 mV.
Application example 6
RuSe prepared in example 6 as shown in application example 12The electrocatalyst is used for preparing hydrogen by electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L, and the anode of the electrocatalyst is used for preparing hydrogen by electrocatalysis in KOH electrolyte with the current density of 10mA/cm2An overpotential of 48mV for the electrocatalyst.
Application example 7
RuSe prepared in example 7 as shown in application example 12The electrocatalyst is used for preparing hydrogen by electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L, and the anode of the electrocatalyst is used for preparing hydrogen by electrocatalysis in KOH electrolyte with the current density of 10mA/cm2An overpotential of 40mV for the electrocatalyst.
Application example 8
RuSe prepared in example 8 as shown in application example 12The electrocatalyst is used for preparing hydrogen by electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L, and the anode of the electrocatalyst is used for preparing hydrogen by electrocatalysis in KOH electrolyte with the current density of 10mA/cm2An overpotential of 51mV for the electrocatalyst.
Application example 9
RuSe prepared in example 9 as shown in application example 12The electrocatalyst is used for preparing hydrogen by electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L, and the anode of the electrocatalyst is used for preparing hydrogen by electrocatalysis in KOH electrolyte with the current density of 10mA/cm2An overpotential of 45mV for the electrocatalyst.
Application example 10
RuSe prepared in comparative example 1 as shown in application example 12The electrocatalyst is used for preparing hydrogen by electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L, and the anode of the electrocatalyst is used for preparing hydrogen by electrocatalysis in KOH electrolyte with the current density of 10mA/cm2The overpotential was 146mV of electrocatalyst.
Application example 11
RuSe prepared in comparative example 2 as shown in application example 12The electrocatalyst is used for preparing hydrogen by electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L, and the anode of the electrocatalyst is used for preparing hydrogen by electrocatalysis in KOH electrolyte with the current density of 10mA/cm2The overpotential is 109mV of electrocatalyst.
The above-mentioned embodiments are intended to illustrate the technical solutions and advantages of the present invention, and it should be understood that the above-mentioned embodiments are only the most preferred embodiments of the present invention, and are not intended to limit the present invention, and any modifications, additions, equivalents, etc. made within the scope of the principles of the present invention should be included in the scope of the present invention.

Claims (9)

1. A preparation method of a ruthenium selenide nanosphere electrocatalyst is characterized by comprising the following steps: adding RuCl3Dissolving in waterDispersing the solution and selenium source in ethylene glycol, stirring, placing the dispersion in a microwave reactor for microwave reaction, centrifugally washing and vacuum drying the obtained precipitate, and further calcining in a tube furnace to obtain crystalline RuSe2Nanosphere electrocatalysts.
2. The preparation method of the ruthenium selenide nanosphere electrocatalyst according to claim 1, wherein the preparation method comprises the following specific steps:
(1) se powder or H2SeO3Dissolving in ethylene glycol as selenium source, and stirring to disperse completely;
(2) adding RuCl3Slowly adding the mixture into the dispersion liquid obtained in the step (1), ultrasonically stirring the mixture until the mixture is uniformly dispersed, and adjusting the pH value of the solution to be alkaline by using KOH;
(3) reacting the dispersion liquid obtained in the step (2) in a rapid microwave reactor, cooling the obtained product to room temperature, centrifugally washing and drying in vacuum;
(4) putting the product obtained in the step (3) into N2Calcining in an atmosphere tube furnace to obtain the final product of crystalline RuSe2Nanosphere electrocatalysts.
3. The method for preparing ruthenium selenide nanosphere electrocatalyst according to claim 2, wherein in step (1) Se powder or H2SeO3The molar ratio of the compound to the ethylene glycol is as follows: 1: 1000-1: 5000.
4. The method for preparing ruthenium selenide nanospheres electrocatalyst as claimed in claim 2, wherein RuCl added in step (2)3With Se powder or H2SeO3The molar ratio of (A) to (B) is: 1:1 to 1: 3.
5. The method for preparing ruthenium selenide nanosphere electrocatalyst according to claim 2, wherein the pH range of the solution is adjusted in step (2) to: 6 to 10.
6. The method for preparing the ruthenium selenide nanosphere electrocatalyst according to claim 2, wherein the power of the fast microwave reactor in the step (3) is as follows: 600W-1000W, and the reaction time in the rapid microwave reactor is as follows: 2min to 6 min.
7. The method for preparing the ruthenium selenide nanosphere electrocatalyst according to claim 2, wherein the calcination temperature in the tube furnace in the step (4) is as follows: the calcining time is between 200 and 600 ℃ as follows: 1 to 4 hours.
8. A ruthenium selenide nanosphere electrocatalyst prepared according to the method of any one of claims 1-7, wherein the ruthenium selenide nanosphere electrocatalyst is a high crystallinity RuSe having regular morphology2Nanospheres.
9. Use of ruthenium selenide nanosphere electrocatalysts prepared according to the method of any of claims 1-7, for electrocatalytic hydrogen evolution under basic conditions.
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