CN115125576B - Composite selenide electrocatalyst and preparation method and application thereof - Google Patents
Composite selenide electrocatalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a composite selenide electrocatalyst and a preparation method and application thereof, belonging to the technical field of catalystsWherein the catalyst has the formula of CoSe/MoSe 2 The structure is spherical and the diameter is 3 μm. The preparation method comprises the following steps: preparing a transparent solution; (2) CoMoO 4 Preparing a precursor; (3) CoSe/MoSe 2 And (4) preparing an electrocatalyst. The invention also discloses the application of the cobalt selenide/molybdenum diselenide composite selenide electrocatalyst in the electro-catalytic cracking of seawater to produce hydrogen. The invention provides CoSe/MoSe 2 The electrocatalyst has the advantages of uniform size, regular appearance, large specific surface area, interface compatibility, high activity and stability. In addition, the preparation method has the advantages of mild preparation conditions, simple operation, strong repeatability and low requirements on instruments and equipment, and provides good technical basis and material guarantee for large-area application.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a cobalt selenide/molybdenum diselenide composite selenide sea water catalyst and a preparation method and application thereof.
Background
The electro-catalytic cracking seawater hydrogen production provides an effective way for solving the energy crisis and developing new energy. The reasonable design of the electro-catalyst material is the key for realizing the high-efficiency electro-catalytic cracking of the seawater to produce hydrogen. Noble metal materials (such as platinum and iridium) have unique advantages, such as easy adsorption/desorption of hydrogen atoms to generate hydrogen, good conductivity, and become one of the leading research hotspots in the field of electrocatalytic water cracking. In view of their scarce reserves and high prices, noble metal materials cannot be used on a large scale. Therefore, it becomes important to find a non-noble metal-based electrocatalyst that is economically efficient.
With the benefit of unique electronic structure and abundant reserves, transition metal-based nanomaterials, especially non-noble metal nano electrocatalysts, have been extensively studied. In recent years, transition metal chalcogenides (e.g., coSe) 2 、MoSe 2 、NiSe 2 ) Have been widely studied due to their low cost and good electrochemical catalytic performance. Wherein the MoSe has a nearly optimal free energy for hydrogen adsorption 2 Are considered to be effective substitutes for Pt. However, moSe 2 The conductivity of the catalyst is poor, so that the performance of the catalyst is not excellent enough when water is subjected to electrocatalytic cracking.
Therefore, how to provide an economic and efficient electrocatalyst synthesis method to promote MoSe 2 The rapid development of the base material in the field of electrocatalytic cracking of seawater and the ultimate realization of industrialization thereof are technical problems that need to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to provide a cobalt selenide/molybdenum diselenide composite selenide electrocatalyst which has uniform size, regular shape, large specific surface area, interface compatibility, higher activity and stability, and a preparation method and application thereof, so as to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following scheme:
a composite selenide electrocatalyst with the molecular formula of CoSe/MoSe 2 The structure is spherical and the diameter is 3 μm.
Has the beneficial effects that: in the electrocatalyst provided by the invention, coSe and MoSe 2 Has synergistic effect, can optimize the electronic structure of single component, improve the conductivity of single component and accelerate the transfer speed of electrons. Water molecules in the seawater are adsorbed on the surface of the catalyst, the water molecules obtain electrons to generate hydrogen protons, and then the two hydrogen protons are combined to generate hydrogen.
A preparation method of the composite selenide electrocatalyst comprises the following steps:
(1) Dropwise adding the amine molybdate tetrahydrate solution into the cobalt chloride hexahydrate solution, continuously and uniformly stirring, adding urea, and uniformly stirring again to obtain a mixed solution;
(2) Reacting the mixed solution at 50-150 ℃ for 10-24h, and then sequentially filtering, washing, vacuum drying and grinding the obtained solid product to obtain the productCoMoO 4 A precursor;
(3) Subjecting the CoMoO to 4 Dispersing the precursor in deionized water to obtain CoMoO 4 Adding selenium powder and sodium borohydride into the precursor suspension in sequence for mixing reaction, and filtering, washing, vacuum drying and grinding the obtained solid product in sequence to obtain CoSe/MoSe 2 An electrocatalyst.
Has the advantages that: coSe/MoSe in the invention 2 The electrocatalyst has porous and flaky shapes, can provide rich active sites, and further shows excellent electrocatalytic hydrogen production activity and stability.
Preferably, the dropwise adding speed in the step (1) is 1 drop/s;
the concentration of the cobalt chloride hexahydrate solution is 0.01-0.10mol/L;
the concentration of the amine molybdate tetrahydrate solution is 0.01-0.10mol/L;
the molar ratio of the cobalt chloride hexahydrate to the ammonium molybdate tetrahydrate is 1 (0.1-5.0);
the concentration of urea in the mixed solution is 0.01-0.15 mol/L.
Has the advantages that: the raw material is CoMoO 4 The synthesis of (a) provides a cobalt source and a molybdenum source.
Preferably, the continuous stirring speed in the step (1) is 300-500 r/min, the time is 0.5-3h, and the temperature is 20-100 ℃;
has the advantages that: the stirring conditions can accelerate the ammonium molybdate tetrahydrate solution and the cobalt chloride hexahydrate solution to dissolve in each other.
Preferably, the re-stirring speed in the step (1) is 300-500 r/min, the time is 10-24h, and the temperature is 50-150 ℃.
Has the beneficial effects that: the above conditions can provide high temperature conditions for the reaction in step (2).
Preferably, the CoMoO in step (2) 4 The concentration of the dispersion liquid is 0.01-0.10mol/L;
the CoMoO 4 The mass ratio of the selenium powder to the sodium borohydride is (0.1-5.0) as follows: (0.1-5.0).
Has the beneficial effects that: the above raw materials provide a selenium source and a reducing agent.
Preferably, the mixing reaction in step (3) is: stirring at 0-100 deg.c for 0-0.5 hr, heating to 100-200 deg.c and reacting for 10-24 hr.
Has the beneficial effects that: under the condition of the process parameters, the selenization reaction can be ensured.
Preferably, in the steps (2) and (3), the washing is respectively carried out for 3 to 5 times by using deionized water and an ethanol solution, and the concentration of the ethanol solution is 99.5 percent;
the vacuum drying temperature is 5-100 ℃, the time is 8-72h, and the vacuum degree is 133 pa-267 pa;
has the advantages that: the above conditions provide a vacuum drying environment to dry the sample.
An application of composite selenide electro-catalyst in the electro-catalytic cracking of seawater for producing hydrogen.
Has the advantages that: the performance of the electrocatalyst in the electro-catalytic cracking of the seawater for hydrogen production is obtained through testing, and the electrocatalyst can be used for the electro-catalytic cracking of the seawater for hydrogen production.
Preferably, the CoSe/MoSe is prepared 2 The dispersed liquid drops of the electrocatalyst are taken as working electrodes on the glassy carbon electrode; a calomel electrode is used as a reference electrode; the graphite electrode is used as a counter electrode; the electrolyte is alkaline seawater; the pH value of the electrolyte is 10-14;
wherein the CoSe/MoSe is 2 The solvent of the electrocatalysis dispersion liquid is water, the concentration is 10mg/mL, and the CoSe/MoSe is 2 The loading capacity of the electrocatalyst on the glassy carbon electrode is 0.05-0.5 mg/cm 2 。
Preferably, the seawater is alkaline seawater (KOH + true seawater), wherein the true seawater is obtained from yellow sea of China, and the concentration of KOH is 1.0mol/L.
The above conditions are the test conditions, as well as the source of seawater and the loading of the sample.
The invention discloses a composite selenide electrocatalyst and a preparation method and application thereof, and CoSe/MoSe provided by the invention 2 The electrocatalyst has the advantages of uniform size, regular appearance, large specific surface area, interface compatibility and high performanceThe activity and stability of the catalyst have excellent hydrogen production performance in alkaline seawater. In addition, the invention pairs CoSe/MoSe through a simple aqueous phase synthesis method 2 The electrocatalyst is prepared under mild preparation conditions, is simple to operate, has strong repeatability and low requirements on instruments and equipment, and provides good technical basis and material guarantee for large-area application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a CoMoO prepared in example 1 4 An X-ray diffraction spectrum of the precursor powder;
FIG. 2 is CoSe/MoSe prepared in example 1 2 An X-ray diffraction pattern of the electrocatalyst powder;
FIG. 3 is CoSe/MoSe prepared in example 1 2 Simulation structure diagram of the electrocatalyst;
FIG. 4 is CoSe/MoSe prepared in example 1 2 Scanning electron microscopy images of the electrocatalyst;
FIG. 5 is CoSe/MoSe prepared in example 1 2 An X-ray photoelectron spectrum of the electrocatalyst;
FIG. 6 is CoSe/MoSe prepared in example 1 2 An X-ray photoelectron high-resolution spectrogram of the electrocatalyst;
FIG. 7 is CoSe/MoSe prepared in example 1 2 The electro-catalyst is used for cracking the seawater hydrogen production performance diagram in the alkaline seawater.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below.
Example 1
A preparation method of the composite selenide electrocatalyst comprises the following steps:
(1) Dissolving cobalt chloride hexahydrate in deionized water at room temperature to obtain a pink transparent cobalt chloride hexahydrate solution, wherein the concentration of the cobalt chloride hexahydrate solution is 0.012mol/L;
(2) At room temperature, dissolving ammonium molybdate tetrahydrate in deionized water to ensure that the concentration of ammonium molybdate tetrahydrate is 0.05mol/L, and obtaining a colorless and transparent ammonium molybdate tetrahydrate solution;
(3) Dropwise adding the amine molybdate tetrahydrate solution in the step (2) into the cobalt chloride hexahydrate solution in the step (1) at the dropping speed of 1 drop/s, enabling the molar ratio of the amine molybdate tetrahydrate solution in the aqueous solution to the cobalt chloride hexahydrate solution in the step (1) to be 1;
(4) Adding urea into the transparent solution obtained in the step (3), and continuously stirring for 1 hour at the stirring speed of 300-500 r/min at the temperature of 30 ℃ to obtain a red transparent solution, wherein the concentration of the urea in the red transparent solution is 0.10mol/L;
(5) Transferring the red transparent solution in the step (4) into a reaction kettle, reacting for 10 hours at 110 ℃ to obtain pink solid, filtering, collecting the solid, fully washing with deionized water and ethanol, performing vacuum drying, and grinding to obtain red powdery CoMoO 4 A precursor;
(6) The CoMoO obtained in the step (5) is treated 4 Dispersing in deionized water to obtain pink suspension;
(7) Adding selenium powder and sodium borohydride into the suspension obtained in the step (6), and continuously stirring for 0.1 hour at the temperature of 0 ℃ to obtain black suspension, whereinSelenium powder, sodium borohydride and CoMoO in the step (5) 4 The mass ratio of (A) to (B) is 2:2:1;
(8) Transferring the solution in the step (7) into a reaction kettle, reacting for 22 hours at 160 ℃ to obtain black solid, filtering, collecting the solid, fully washing with deionized water and ethanol, performing vacuum drying, and grinding to obtain black powdery CoSe/MoSe 2 An electrocatalyst;
as can be seen from the powder X-ray diffraction spectrum of FIG. 1, the prepared product has CoMoO 4 The crystal structure of (a); as can be seen from the powder X-ray diffraction spectrum of FIG. 2, the structural formulas of the prepared product are CoSe and MoSe 2 ；
Through further calculation, a structure model of the prepared product is simulated as shown in fig. 3, and the small ball model sequentially represents selenium, molybdenum, selenium, cobalt and selenium atoms from top to bottom, so that the product has good interface compatibility;
the synthesized CoSe/MoSe can be seen from the scanning electron microscope picture of FIG. 4 2 The catalyst sample has good uniformity and is of a spherical structure, and the diameter of the catalyst sample is about 3 microns;
it can be seen in the X-ray photoelectron spectrum of fig. 5 that the three elements of cobalt, molybdenum and selenium in the catalyst obviously exist, and the purity of the sample is high;
in the X-ray photoelectron fine spectrum of FIG. 6, different chemical valence states among elements can also be seen in the scanning spectra of cobalt, molybdenum and selenium of the material.
Example 2
A preparation method of the composite selenide electrocatalyst comprises the following steps:
(1) Dissolving cobalt chloride hexahydrate in deionized water at room temperature to obtain a pink transparent cobalt chloride hexahydrate solution, wherein the concentration of the cobalt chloride hexahydrate solution is 0.012mol/L;
(2) At room temperature, dissolving ammonium molybdate tetrahydrate in deionized water to ensure that the concentration of ammonium molybdate tetrahydrate is 0.05mol/L, and obtaining a colorless and transparent ammonium molybdate tetrahydrate solution;
(3) Dropwise adding the amine molybdate tetrahydrate solution in the step (2) into the cobalt chloride hexahydrate solution in the step (1) at the dropping speed of 1 drop/s, enabling the molar ratio of the amine molybdate tetrahydrate solution in the aqueous solution to the cobalt chloride hexahydrate solution in the step (1) to be 1;
(4) Adding urea into the transparent solution obtained in the step (3), and continuously stirring for 1 hour at the temperature of 30 ℃ and at the stirring speed of 300-500 r/min to obtain a red transparent solution, wherein the concentration of the urea in the red transparent solution is 0.10mol/L;
(5) Transferring the red transparent solution in the step (4) into a reaction kettle, reacting for 10 hours at 110 ℃ to obtain pink solid, filtering, collecting the solid, fully washing with deionized water and ethanol, performing vacuum drying, and grinding to obtain red powdery CoMoO 4 A precursor;
(6) The CoMoO obtained in the step (5) is treated 4 Dispersing in deionized water to obtain pink suspension;
(7) Adding selenium powder and sodium borohydride into the suspension obtained in the step (6), and continuously stirring for 0.1 hour at the temperature of 0 ℃ to obtain black suspension, wherein the selenium powder, the sodium borohydride and the CoMoO obtained in the step (5) 4 The mass ratio of (A) to (B) is 2:2:1;
(8) Transferring the solution in the step (7) into a reaction kettle, reacting for 10 hours at 160 ℃ to obtain black solid, filtering, collecting the solid, fully washing with deionized water and ethanol, performing vacuum drying, and grinding to obtain black powdery CoSe/MoSe 2 An electrocatalyst.
Example 3
A preparation method of the composite selenide electrocatalyst comprises the following steps:
(1) Dissolving cobalt chloride hexahydrate in deionized water at room temperature to obtain a pink transparent cobalt chloride hexahydrate solution, wherein the concentration of the cobalt chloride hexahydrate solution is 0.012mol/L;
(2) At room temperature, dissolving ammonium molybdate tetrahydrate in deionized water to ensure that the concentration of ammonium molybdate tetrahydrate is 0.05mol/L, and obtaining a colorless and transparent ammonium molybdate tetrahydrate solution;
(3) Dropwise adding the amine molybdate tetrahydrate solution in the step (2) into the cobalt chloride hexahydrate solution in the step (1) at the dropping speed of 1 drop/s, enabling the molar ratio of the amine molybdate tetrahydrate solution in the aqueous solution to the cobalt chloride hexahydrate solution in the step (1) to be 1;
(4) Adding urea into the transparent solution obtained in the step (3), and continuously stirring for 1 hour at the temperature of 30 ℃ and at the stirring speed of 300-500 r/min to obtain a red transparent solution, wherein the concentration of the urea in the red transparent solution is 0.10mol/L;
(5) Transferring the red transparent solution in the step (4) into a reaction kettle, reacting for 10 hours at 110 ℃ to obtain pink solid, filtering, collecting the solid, fully washing with deionized water and ethanol, performing vacuum drying, and grinding to obtain red powdery CoMoO 4 A precursor;
(6) The CoMoO obtained in the step (5) is treated 4 Dispersing in deionized water to obtain pink suspension;
(7) Adding selenium powder and sodium borohydride into the suspension obtained in the step (6), and continuously stirring for 0.1 hour at the temperature of 0 ℃ to obtain black suspension, wherein the selenium powder, the sodium borohydride and the CoMoO obtained in the step (5) 4 The mass ratio of (2): 2:1;
(8) Transferring the solution in the step (7) into a reaction kettle, reacting for 17 hours at 160 ℃ to obtain black solid, filtering, collecting the solid, fully washing with deionized water and ethanol, performing vacuum drying, and grinding to obtain black powdery CoSe/MoSe 2 An electrocatalyst.
Example 4
A preparation method of the composite selenide electrocatalyst comprises the following steps:
(1) Dissolving cobalt chloride hexahydrate in deionized water at room temperature to obtain a pink transparent cobalt chloride hexahydrate solution, wherein the concentration of the cobalt chloride hexahydrate solution is 0.012mol/L;
(2) At room temperature, dissolving ammonium molybdate tetrahydrate in deionized water to ensure that the concentration of ammonium molybdate tetrahydrate is 0.05mol/L, and obtaining a colorless and transparent ammonium molybdate tetrahydrate solution;
(3) Dropwise adding the amine molybdate tetrahydrate solution in the step (2) into the cobalt chloride hexahydrate solution in the step (1) at the dropping speed of 1 drop/s, enabling the molar ratio of the amine molybdate tetrahydrate solution in the aqueous solution to the cobalt chloride hexahydrate solution in the step (1) to be 1;
(4) Adding urea into the transparent solution obtained in the step (3), and continuously stirring for 1 hour at the temperature of 30 ℃ and at the stirring speed of 300-500 r/min to obtain a red transparent solution, wherein the concentration of the urea in the red transparent solution is 0.10mol/L;
(5) Transferring the red transparent solution in the step (4) into a reaction kettle, reacting for 10 hours at 110 ℃ to obtain pink solid, filtering, collecting the solid, fully washing with deionized water and ethanol, performing vacuum drying, and grinding to obtain red powdery CoMoO 4 A precursor;
(6) The CoMoO obtained in the step (5) is treated 4 Dispersing in deionized water to obtain pink suspension;
(7) Adding selenium powder and sodium borohydride into the suspension obtained in the step (6), and continuously stirring for 0.1 hour at the temperature of 0 ℃ to obtain black suspension, wherein the selenium powder, the sodium borohydride and the CoMoO obtained in the step (5) 4 The mass ratio of (2): 2:1;
(8) Transferring the solution in the step (7) into a reaction kettle, reacting for 24 hours at 160 ℃ to obtain black solid, filtering, collecting the solid, fully washing with deionized water and ethanol, performing vacuum drying, and grinding to obtain black powdery CoSe/MoSe 2 An electrocatalyst.
And (3) performance testing:
CoSe/MoSe 2 The application of the electrocatalyst in the electro-catalytic cracking of seawater for hydrogen production:
(1) Mixing CoSe/MoSe 2 The dispersed liquid of the electrocatalyst is dropped on the glassy carbon electrode to be used as a working electrode; calomel electrode asA reference electrode; the graphite electrode served as the counter electrode. Wherein, coSe/MoSe 2 The solvent of the electrocatalyst dispersion liquid is water, the concentration is 10mg/mL, coSe/MoSe 2 The loading capacity of the electrocatalyst on the glassy carbon electrode is 0.35mg/cm 2 。
(2) The electrolyte tested in examples 1-4 was alkaline seawater (KOH + true seawater), wherein the true seawater was obtained from yellow sea of China, and the concentration of KOH was 1.0mol/L. The test results are shown in table 1.
TABLE 1 CoSe/MoSe 2 Electrocatalytic performance of electrocatalyst
As can be seen in combination with Table 1 above, coSe/MoSe 2 The method has excellent performance of producing hydrogen by electro-catalytically cracking seawater when the reaction time is 22 hours, and is specifically shown in figure 7.
The above-described embodiments are only intended to illustrate the preferred embodiments of the present invention, and not to limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.
Claims (7)
1. A preparation method of the composite selenide electrocatalyst is characterized by comprising the following steps:
(1) Dropwise adding the amine molybdate tetrahydrate solution into the cobalt chloride hexahydrate solution, continuously and uniformly stirring, adding urea, and uniformly stirring again to obtain a mixed solution;
the concentration of the cobalt chloride hexahydrate solution in the step (1) is 0.01-0.10mol/L;
the concentration of the amine molybdate tetrahydrate solution is 0.01-0.10mol/L;
the molar ratio of the cobalt chloride hexahydrate to the ammonium molybdate tetrahydrate is 1 (0.1-5.0);
the concentration of urea in the mixed solution is 0.01-0.15 mol/L;
(2) Placing the mixed solution into a reaction kettle, reacting for 10-24h at 110-150 ℃, and then sequentially filtering, washing, vacuum drying and grinding the obtained solid product to obtain the CoMoO 4 A precursor;
(3) Subjecting the CoMoO to 4 Dispersing the precursor in deionized water to obtain CoMoO 4 Adding selenium powder and sodium borohydride into the precursor suspension in sequence for mixing reaction, and filtering, washing, vacuum drying and grinding the obtained solid product in sequence to obtain CoSe/MoSe 2 An electrocatalyst;
the CoMoO in the step (3) 4 The concentration of the precursor suspension is 0.01-0.10mol/L;
the CoMoO 4 The mass ratio of the precursor, the selenium powder and the sodium borohydride is 1 (0.1-5.0): (0.1 to 5.0);
the mixing reaction in the step (3) is as follows: stirring at 0-100 deg.c for 0-0.5 hr, transferring the solution to a reactor, and heating to 100-200 deg.c for 10-24 hr.
2. The method for preparing the composite selenide electrocatalyst according to claim 1, wherein the continuous stirring rate in the step (1) is 300-500 r/min, the time is 0.5-3h, and the temperature is 20-100 ℃.
3. The method for preparing the composite selenide electrocatalyst according to claim 1, wherein the re-stirring rate in the step (1) is 300-500 r/min, the time is 10-24h, and the temperature is 50-150 ℃.
4. The method for preparing the composite selenide electrocatalyst according to claim 1, wherein the washing in steps (2) and (3) is 3-5 times by using deionized water and ethanol solution, respectively, the concentration of the ethanol solution is 99.5%;
the vacuum drying temperature is 5-100 ℃, the time is 8-72h, and the vacuum degree is 133-267 pa.
5. A composite selenide electrocatalyst prepared by the method for preparing a composite selenide electrocatalyst according to any one of claims 1 to 4, wherein the chemical composition of the electrocatalyst is CoSe/MoSe 2 The structure is spherical and the diameter is 3 μm.
6. The use of the composite selenide electrocatalyst according to claim 5 in the electro-catalytic cracking of seawater to produce hydrogen.
7. Use according to claim 6, wherein the CoSe/MoSe is applied 2 The dispersed liquid drops of the electrocatalyst are taken as working electrodes on the glassy carbon electrode; a calomel electrode is used as a reference electrode; the graphite electrode is used as a counter electrode; the electrolyte is alkaline seawater;
wherein the CoSe/MoSe is 2 The concentration of the electro-catalyst dispersion liquid is 10mg/mL, and the CoSe/MoSe is 2 The loading capacity of the electrocatalyst on the glassy carbon electrode is 0.05-0.5 mg/cm 2 。
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| CN109092331A (en) * | 2018-08-04 | 2018-12-28 | 安徽师范大学 | A kind of hollow tubular cobalt selenium compound/molybdenum selenium compound composite nano materials and its preparation method and application |
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| CN107051550A (en) * | 2017-04-24 | 2017-08-18 | 山东大学 | A kind of electro-catalysis water decomposition MoSe2/Co0.85Se composites and preparation method and application |
| CN109092331A (en) * | 2018-08-04 | 2018-12-28 | 安徽师范大学 | A kind of hollow tubular cobalt selenium compound/molybdenum selenium compound composite nano materials and its preparation method and application |
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