CN113649027A - Catalyst for chlorine evolution reaction in chlor-alkali industry and preparation method thereof - Google Patents
Catalyst for chlorine evolution reaction in chlor-alkali industry and preparation method thereof Download PDFInfo
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- CN113649027A CN113649027A CN202010380340.7A CN202010380340A CN113649027A CN 113649027 A CN113649027 A CN 113649027A CN 202010380340 A CN202010380340 A CN 202010380340A CN 113649027 A CN113649027 A CN 113649027A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 26
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000000460 chlorine Substances 0.000 title claims abstract description 20
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000003513 alkali Substances 0.000 title abstract description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 16
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 14
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 14
- 239000010937 tungsten Substances 0.000 claims abstract description 14
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004729 solvothermal method Methods 0.000 claims abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000012046 mixed solvent Substances 0.000 claims abstract description 3
- 230000001376 precipitating effect Effects 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract 2
- 239000000463 material Substances 0.000 claims description 18
- 239000002135 nanosheet Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 239000011669 selenium Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002086 nanomaterial Substances 0.000 claims 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 22
- 238000009776 industrial production Methods 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 12
- 238000002484 cyclic voltammetry Methods 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 9
- 238000003795 desorption Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000011056 performance test Methods 0.000 description 7
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000012279 sodium borohydride Substances 0.000 description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 description 6
- SDDGNMXIOGQCCH-UHFFFAOYSA-N 3-fluoro-n,n-dimethylaniline Chemical compound CN(C)C1=CC=CC(F)=C1 SDDGNMXIOGQCCH-UHFFFAOYSA-N 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 238000004108 freeze drying Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000010411 electrocatalyst Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- QYGMYMCIOLTWMT-UHFFFAOYSA-N [Re]=[Se] Chemical compound [Re]=[Se] QYGMYMCIOLTWMT-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- -1 transition metal sulfur group compound Chemical class 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- ULSAYCVVCOFSKH-UHFFFAOYSA-N N.[Re+4] Chemical compound N.[Re+4] ULSAYCVVCOFSKH-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J37/16—Reducing
-
- 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
- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
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- 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
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- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
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Abstract
The invention discloses a catalyst for an anodic chlorine evolution reaction of electrolytic salt water in the chlor-alkali industry and a preparation method thereof. The preparation method adopts a high-temperature solvothermal method: dissolving selenium powder, tungsten-based inorganic salt, rhenium-based inorganic salt and a reducing agent in a mixed solvent of N, N-dimethylformamide and water, reacting the mixed solution at high temperature and high pressure, cooling to room temperature, separating, precipitating and drying to obtain the catalyst. The catalyst obtained by the invention has excellent catalytic activity, catalytic selectivity and stability in an acidic electrolyte, has the characteristics of low cost and simple and feasible preparation method, and is suitable for industrial production.
Description
Technical Field
The invention relates to an electrocatalyst for chlorine evolution reaction of an anode in chlor-alkali industry and a preparation method thereof, in particular to a catalyst with a three-dimensional porous structure formed by stacking transition metal (tungsten, rhenium) selenide nanosheets.
Background
Chlorine, one of the most important industrial chemicals, is a key chemical in the production of polymers and pharmaceuticals, in the paper industry and in water treatment, with a global annual production of about 7500 million tons. For example, an average of approximately 1000 million tons of chlorine are consumed in europe for the production of disinfectants and other industrial products each year. The chlor-alkali industry refers to the electrolysis of aqueous sodium chloride solutions to produce sodium hydroxide, chlorine and hydrogen, and is the major route for the industrial production of chlorine at present. In the process, chloride ions are oxidized at the anode to generate chlorine, and chlorine precipitation reaction is carried out; a reduction reaction occurs at the cathode to produce hydrogen gas and sodium hydroxide.
In the chlor-alkali industry, mixed metal oxides of noble metals (iridium or ruthenium) are mainly used as electrocatalysts at anodes where the chlorine evolution reaction takes place, such as dimensionally stable anodes (mixed solid solution of 30% ruthenium dioxide and 70% titanium dioxide). However, theoretical simulations and experimental studies show that: (1) the catalyst has high catalytic activity of oxygen precipitation reaction. There is a competitive relationship between the oxygen evolution reaction and the chlorine evolution reaction, both of which are catalyzed on similar active sites on the catalyst surface. Therefore, the mixed metal oxide catalyst has low reaction selectivity, and influences the catalytic activity of the catalyst on chlorine gas precipitation and the purity of a product; (2) the mixed metal oxide catalyst contains a large amount of noble metal elements, and the preparation cost is high; (3) at present, the industrial mixed metal oxide catalyst is a block porous material, and the surface area and the utilization rate of the catalyst are to be further improved. Therefore, the development of the non-noble metal chlorine evolution reaction catalyst with high catalytic selectivity, high catalytic activity, high utilization rate and low cost has important significance for the sustainable development of the chlor-alkali industry.
Disclosure of Invention
The invention aims to provide an electrocatalyst applied to the chlorine evolution reaction of an anode in the chlor-alkali industry, which is a non-noble metal composite catalyst obtained by carrying out solvothermal reaction on a mixed solution of a precursor material and a reducing agent material under the conditions of high temperature and high pressure, and reduces the cost of the catalyst on the premise of ensuring the catalytic activity, catalytic selectivity and stability of the catalyst.
The electrocatalyst for the chlorine evolution reaction of the anode in the chlor-alkali industry provided by the invention has a three-dimensional porous structure. Specifically, transition metal sulfur group compound nano sheets are mutually staggered to form a three-dimensional structure.
The transition metal sulfur group compound nanosheet is of a two-dimensional layered structure, and comprises the following components: rhenium selenide, tungsten selenide, and tungsten selenide/rhenium.
In the tungsten selenide/rhenium nanosheet structure, the atomic ratio of the tungsten element in the total amount of the metal cation element is 0% to 100%, and the atomic ratio of the rhenium element in the total amount of the metal cation element is 0% to 100%.
The thickness of the transition metal sulfur group compound nano-sheet is preferably in the range of 1-20 nm.
The invention also provides a preparation method of the catalyst, which mainly adopts a high-temperature solvothermal method and comprises the following steps:
1) dissolving selenium powder, tungsten-based inorganic salt, rhenium-based inorganic salt and a reducing agent in a mixed solvent of N, N-dimethylformamide and water;
2) reacting the mixed solution obtained in the step 1) under the conditions of high temperature and high pressure, and separating, precipitating and drying after cooling to room temperature to obtain the catalyst;
in the mixed solution obtained in the step 1), the concentration of the selenium powder substances is 10-100 mmol/L; the concentration of the reducing agent is preferably 0.01-0.1 mmol/L; the concentration of the tungsten-based inorganic salt is preferably 0-50 mmol/L; the concentration of the rhenium-based inorganic salt is preferably 0 to 50 mmol/L. The tungsten-based inorganic salt species is preferably sodium tungstate, the rhenium-based inorganic salt is preferably ammonium perrhenate, and the reducing agent is preferably sodium borohydride.
In the step 2), the reaction temperature is 180-240 ℃. The reaction time is 12-72 hours.
In the preparation of the catalyst, firstly, the tungsten-based inorganic salt, the selenium powder and the reducing agent are dissolved in N, N-dimethylformamide, and then the solution is mixed and stirred with the water solution fully dissolved with the rhenium-based inorganic salt for 2 hours to obtain a uniform mixed solution. The step has the advantages of helping the precursor material to be uniformly distributed in the solution, and further forming a nanosheet structure with uniform thickness and uniform element distribution in the high-temperature high-pressure treatment process. And then, nucleating and growing the mixed solution under the conditions of high temperature and high pressure to ensure that ions in the material gradually grow into a two-dimensional nanosheet material, and stacking to form a three-dimensional porous structure. In the preparation process, the proportion of the rhenium-based inorganic salt and the tungsten-based inorganic salt in the precursor material can be adjusted to realize any proportion of the rhenium element and the tungsten element in the final product.
The preparation method of the catalyst is simple and feasible, and is suitable for industrial production. Experiments prove that the catalyst material obtained from the reactant system of 200mg to 10g has consistent object image and appearance, so that the material is suitable for industrial production of large-scale quantities.
The performance test of the prepared catalyst proves that the voltage value of the catalyst is similar to that of the commercial catalyst. And the Tafel slope of the material is small, which shows that the material has good dynamic characteristics. In addition, after the stability test is carried out on the material, the obtained material still maintains excellent catalytic activity after long-term work.
Drawings
FIG. 1 is a diagram of the synthesis of the catalyst of the present invention, after nucleation, aggregate growth, and maturation steps, the final catalyst is obtained.
Fig. 2 is a transmission electron microscope image of tungsten selenide nanosheets.
Fig. 3 is a transmission electron microscope image of rhenium selenide nanosheets.
Fig. 4 is a transmission electron micrograph, a nitrogen desorption curve, and a catalytic performance test curve of the catalyst material No. 1, in which: the method comprises the following steps of (a) showing a transmission electron microscope, (b) showing a nitrogen adsorption and desorption curve, (c) showing cyclic voltammograms at different scanning speeds, (d) selecting data of the cyclic voltammograms at different scanning speeds, (e) showing a catalytic performance test curve, and (f) showing a tafel curve.
Fig. 5 is a transmission electron micrograph, a nitrogen desorption curve, and a catalytic performance test curve of catalyst material No. 2, wherein: the method comprises the following steps of (a) showing a transmission electron microscope, (b) showing a nitrogen adsorption and desorption curve, (c) showing cyclic voltammograms at different scanning speeds, (d) selecting data of the cyclic voltammograms at different scanning speeds, (e) showing a catalytic performance test curve, and (f) showing a tafel curve.
Fig. 6 is a transmission electron micrograph, a nitrogen desorption curve, and a catalytic performance test curve of the catalyst material No. 3, in which: the method comprises the following steps of (a) showing a transmission electron microscope, (b) showing a nitrogen adsorption and desorption curve, (c) showing cyclic voltammograms at different scanning speeds, (d) selecting data of the cyclic voltammograms at different scanning speeds, (e) showing a catalytic performance test curve, and (f) showing a tafel curve.
FIG. 7 is a plot of cyclic voltammograms of catalyst 3(a) in different solutions and (b) the time stability.
Fig. 8 is an atomic force microscope picture of catalyst 3.
Fig. 9 is a transmission electron microscope diffraction image and an element distribution image of the catalyst 3. (a) Diffraction images of catalyst 3, and (b-f) high angle dark field electron micrographs and corresponding elemental distribution maps of catalyst 3.
Detailed Description
The present invention will be further described with reference to the following examples, but the scope of the present invention is not limited to these examples.
EXAMPLE I preparation of tungsten selenide nanosheet network Structure
2mmol of selenium powder, 0.05mmol of sodium borohydride and 1mmol of sodium tungstate are simultaneously dissolved in 20mL of N, N-dimethyl formamide, ultrasonic dispersion is carried out for 30 minutes, then the mixture is transferred into a reaction kettle, and then solvothermal reaction is carried out for 24 hours at 220 ℃. Cooling to room temperature, washing, and freeze-drying. The transmission electron microscope image of the nanosheet is shown in fig. 2.
EXAMPLE II preparation of rhenium selenide nanosheet network Structure
Dissolving 2mmol of selenium powder and 0.05mmol of sodium borohydride in 20mL of N, N-dimethylformamide simultaneously; 1mmol of ammonium perrhenate was dissolved in 10mL of deionized water, and the two solutions were ultrasonically dispersed for 30 minutes and then mixed well. The above solution was transferred to a reaction vessel, followed by a solvothermal reaction at 220 ℃ for 24 hours. Cooling to room temperature, washing, and freeze-drying. The transmission electron microscope image of the nanosheet is shown in fig. 3.
EXAMPLE III preparation of catalyst 1 and Performance testing
Dissolving 2mmol of selenium powder, 0.05mmol of sodium borohydride and x mmol (x is more than 0 and less than 1) of sodium tungstate in 20mL of N, N-dimethylformamide simultaneously; (1-x) mmol of ammonium perrhenate was dissolved in 10mL of deionized water, and the two solutions were ultrasonically dispersed for 30 minutes and then mixed well. The above solution was transferred to a reaction vessel, followed by solvothermal reaction at 240 ℃ for 48 hours. Cooling to room temperature, washing, and freeze-drying. Specific values of x and the amount of precursor used are shown below,
the catalyst obtained in example three was subjected to a test for catalytic performance of chlorine evolution reaction. By comparing the catalyst performances of different cation ratios, the catalyst can be subjected to the solvothermal reaction at 240 ℃ for 48 hours, wherein the catalytic performance is the best when the molar charge ratio of the sodium tungstate to the high ammonium rhenium salt is 1: 3, and the catalyst is numbered as 1. The transmission electron microscope photograph of the catalyst No. 1 is shown in fig. 4 (a), and the catalyst is in a nano-sheet structure which is staggered with each other. FIG. 4 (b) shows the nitrogen desorption curve for catalyst No. 1 having a BET specific surface area of 64.91m2(ii) in terms of/g. FIG. 4(c) is a cyclic voltammogram of the catalyst 1 at different sweep rates, and a specific data point is selected to obtain FIG. 4(d), which is calculated to obtain a catalyst capacitance of 7.82e-4F/cm2. As shown in FIGS. 4(e) - (f), the catalyst was at 10mA/cm2The corresponding voltage value at the current density of (1) was 1.48V, and the Tafel slope was 57mV/dec (see Table 1).
EXAMPLE four preparation of catalyst 2 and Performance testing
Dissolving 2mmol of selenium powder, 0.05mmol of sodium borohydride and x mmol (x is more than 0 and less than 1) of sodium tungstate in 20mL of N, N-dimethylformamide simultaneously; (1-x) mmol of ammonium perrhenate was dissolved in 10mL of deionized water, and the two solutions were ultrasonically dispersed for 30 minutes and then mixed well. The above solution was transferred to a reaction kettle, followed by solvothermal reaction at various temperatures for 48 hours. Cooling to room temperature, washing, and freeze-drying. Specific x-values reaction temperatures are shown below.
By comparing different reaction temperatures with different tungstenThe catalyst with the sodium content has good catalytic activity of chlorine precipitation reaction under the condition of 180-240 ℃ and different metal ratios, and the catalyst with the best activity under the condition of 220 ℃ is numbered as 2, and the catalytic activity is shown in table 1. The transmission electron micrograph of the catalyst No. 2 is shown in fig. 5(a), and the morphology thereof is an interdigitated nanosheet structure. FIG. 5 (b) shows a nitrogen desorption curve of the catalyst, and the BET specific surface area of catalyst No. 2 is 69.81m2(ii) in terms of/g. FIG. 5(c) is a cyclic voltammogram of catalyst 2 at different sweep rates, and the specific data points are selected to obtain FIG. 5(d), which is calculated to obtain a catalyst capacitance of 6.17e-4F/cm2. As shown in FIGS. 5(e) - (f), the catalyst was at 10mA/cm2The corresponding voltage value at the current density of (1) was 1.43V, and the Tafel slope was 46 mV/dec.
EXAMPLE V preparation of catalyst 3 and Performance testing
Dissolving 2mmol of selenium powder, 0.05mmol of sodium borohydride and x mmol (x is more than 0 and less than 1) of sodium tungstate in 20mL of N, N-dimethylformamide simultaneously; (1-x) mmol of ammonium perrhenate was dissolved in 10mL of deionized water, and the two were dispersed by ultrasonic for 30 minutes and then mixed well. The above solution was transferred to a reaction kettle, followed by solvothermal reaction at a temperature of 220 ℃ for various reaction times. Cooling to room temperature, washing, and freeze-drying. Specific values of x and reaction time are shown below.
By comparing catalysts with different reaction times and different sodium tungstate contents, the catalyst has good catalytic activity of chlorine precipitation reaction under the condition of reaction time of 12-72 hours and different metal proportions, and the catalyst has the best activity under the condition of 24 hours, wherein the catalyst is numbered as 3, and the catalytic activity is shown in table 1. The transmission electron micrograph of catalyst No. 3 is shown in fig. 6(a), and the morphology thereof is an interdigitated nanosheet structure. FIG. 6 (b) shows a nitrogen desorption curve of the catalyst, and the BET specific surface area of the catalyst No. 3 is 71.63m2(ii) in terms of/g. FIG. 6(c) Selecting specific data points to obtain a graph 6(d) for cyclic voltammetry curves of No. 3 catalyst at different sweep rates, and calculating to obtain the catalyst with the capacitance of 8.02e-4F/cm2. As shown in FIGS. 6(e) - (f), the catalyst was at 10mA/cm2The corresponding voltage value at the current density of (1) was 1.41V, and the Tafel slope was 57 mV/dec. Fig. 7(a) shows that the catalyst No. 3 caused only a chlorine evolution reaction and no oxygen evolution reaction in a mixed aqueous solution of sodium chloride and sulfuric acid, and still maintained good catalytic activity after 35,000s cycles (as shown in fig. 7 (b)). FIG. 8 is an atomic force microscope photograph of catalyst No. 3 with a catalyst lamella thickness of 3 nm. The catalyst material is polycrystalline as shown in fig. 9 (a). Fig. 9(b-f) are high angle dark field electron micrographs and corresponding elemental distribution plots for catalyst 3 demonstrating the uniform distribution of the four elements oxygen, selenium, rhenium, and tungsten on the surface of the material.
TABLE 1 Performance of the catalyst
Claims (10)
1. A catalyst for the chlorine evolution reaction of an electrolytic salt water anode is a three-dimensional porous structure formed by folding nanosheets, and elements of the catalyst comprise tungsten, rhenium, oxygen and selenium.
2. The catalyst of claim 1, wherein the material is a three-dimensional porous structure formed by a stack of pleated two-dimensional layered nanomaterials.
3. The catalyst of claim 1, wherein the nanosheets have a thickness of 1 to 20 nm.
4. The catalyst according to claim 1, wherein the metal element is tungsten, rhenium, or the like.
5. The catalyst of claim 1, wherein the non-metallic element is selenium, oxygen, or the like.
6. The method for preparing the catalyst of any one of claims 1 to 5 comprises the following steps:
1) dissolving selenium powder, tungsten-based inorganic salt, rhenium-based inorganic salt and a reducing agent in a mixed solvent of N, N-dimethylformamide and water;
2) reacting the mixed solution obtained in the step 1) under the conditions of high temperature and high pressure, cooling to room temperature, separating, precipitating and drying to obtain the catalyst.
7. The method according to claim 6, wherein the solvent in step 1) is deionized water, N-dimethylformamide, or a mixture thereof.
8. The method of claim 6, wherein the solvothermal reaction time of the step 2) is 12 to 72 hours.
9. The method according to claim 6, wherein the solvothermal reaction temperature in step 2) is 180-240 ℃.
10. The method according to claim 6, wherein the concentration of the selenium powder is preferably 10 to 100 mmol/L; the concentration of the reducing agent is preferably 0.01-0.1 mmol/L; the concentration of the tungsten-based inorganic salt is preferably 0-50 mmol/L; the concentration of the rhenium-based inorganic salt is preferably 0 to 50 mmol/L.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20110105311A1 (en) * | 2007-08-09 | 2011-05-05 | Yukiyoshi Ueno | Fuel cell electrode catalyst, method for evaluating performance of oxygen-reducing catalyst, and solid polymer fuel cell comprising the fuel cell electrode catalyst |
| US20110111322A1 (en) * | 2007-08-09 | 2011-05-12 | Yukiyoshi Ueno | Fuel cell electrode catalyst, method for evaluating performance of oxygen-reducing catalyst, and solid polymer fuel cell comprising the fuel cell electrode catalyst |
| US20120122666A1 (en) * | 2007-08-09 | 2012-05-17 | Yukiyoshi Ueno | Fuel cell electrode catalyst, method for evaluating performance of oxygen-reducing catalyst, and solid polymer fuel cell comprising the fuel cell electrode catalyst |
| CN105776154A (en) * | 2016-05-10 | 2016-07-20 | 电子科技大学 | Preparation method of tungsten diselenide nanosheet |
| CN105967155A (en) * | 2016-05-10 | 2016-09-28 | 电子科技大学 | Method for preparing tungsten diselenide nanoflower |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20110105311A1 (en) * | 2007-08-09 | 2011-05-05 | Yukiyoshi Ueno | Fuel cell electrode catalyst, method for evaluating performance of oxygen-reducing catalyst, and solid polymer fuel cell comprising the fuel cell electrode catalyst |
| US20110111322A1 (en) * | 2007-08-09 | 2011-05-12 | Yukiyoshi Ueno | Fuel cell electrode catalyst, method for evaluating performance of oxygen-reducing catalyst, and solid polymer fuel cell comprising the fuel cell electrode catalyst |
| US20120122666A1 (en) * | 2007-08-09 | 2012-05-17 | Yukiyoshi Ueno | Fuel cell electrode catalyst, method for evaluating performance of oxygen-reducing catalyst, and solid polymer fuel cell comprising the fuel cell electrode catalyst |
| CN105776154A (en) * | 2016-05-10 | 2016-07-20 | 电子科技大学 | Preparation method of tungsten diselenide nanosheet |
| CN105967155A (en) * | 2016-05-10 | 2016-09-28 | 电子科技大学 | Method for preparing tungsten diselenide nanoflower |
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