CN111889098A - Beta-lead dioxide catalyst with different morphologies as well as preparation method and application thereof - Google Patents
Beta-lead dioxide catalyst with different morphologies as well as preparation method and application thereof Download PDFInfo
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- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000000243 solution Substances 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000003756 stirring Methods 0.000 claims abstract description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 17
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000000725 suspension Substances 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000000967 suction filtration Methods 0.000 claims abstract description 8
- 238000001291 vacuum drying Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000000411 inducer Substances 0.000 claims abstract description 6
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 5
- 230000003213 activating effect Effects 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims description 21
- 230000035484 reaction time Effects 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229940046892 lead acetate Drugs 0.000 claims description 3
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 230000001939 inductive effect Effects 0.000 claims 2
- 239000007788 liquid Substances 0.000 abstract description 16
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000005868 electrolysis reaction Methods 0.000 description 14
- 230000005540 biological transmission Effects 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000004744 fabric Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- 229920000557 Nafion® Polymers 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical class [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229960000502 poloxamer Drugs 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
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Abstract
The invention discloses beta-lead dioxide catalysts with different morphologies and a preparation method and application thereof, wherein the preparation process of the catalysts comprises the following steps: adding inorganic base into the aqueous solution of lead salt, stirring uniformly, adding a structure inducer, and keeping the temperature; and continuously adding a sodium hypochlorite solution to generate a brownish red turbidity, and stirring to uniformly disperse the turbidity to form a turbid liquid. Carrying out hydrothermal reaction on the obtained suspension at the temperature of 85-140 ℃ for 6-12 hours, cooling to room temperature after the reaction is finished, washing for 3-5 times by using absolute ethyl alcohol and deionized water respectively, carrying out suction filtration treatment, drying the obtained product in a vacuum drying oven, and finally activating in a plasma reaction furnace to obtain the beta-lead dioxide catalyst with different shapes. The beta-lead dioxide catalyst prepared by the invention has the advantages of low cost and simple process, is applied to the reaction of preparing ozone by electrolyzing water, has high catalytic activity and stability, and obviously improves the current efficiency of preparing ozone by electrolyzing water.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to a beta-lead dioxide catalyst with different morphologies as well as a preparation method and application thereof.
Background
Ozone is strong in oxidizability, green and environment-friendly, and is stronger than other common oxidants, and is one of the strongest oxidants. Because the product obtained after the ozone reaction is only oxygen, secondary pollutants can not be generated and the environment can not be influenced. It can be said that ozone is a highly environmentally friendly, highly effective, strong oxidant, which is the main reason why ozone is widely used. The application in the aspects of water treatment, medical treatment and the like not only needs strong oxidizing property, but also is important in safety and environmental protection, so that the ozone has both strong oxidizing property and environmental protection property, and has potential great effect.
Ozone has great potential in application, and the production of ozone is particularly important. Electrolytic, corona discharge, ultraviolet irradiation and radiochemical methods are the main routes for the artificial generation of ozone. The radiochemical method is used for generating ozone, raw materials are cheap and easy to obtain, the utilization rate is high, the concentration of the generated ozone is also high, but the radiochemical method has the defects of low safety and high cost of radioactive sources, cannot meet the requirement of industrial mass production, and can only be suitable for some special conditions. Currently, radiochemical methods have been largely eliminated. The production of ozone by the ultraviolet irradiation method is low and energy consumption is high, the output is far lower than the cost input, and the method is not suitable for industrial mass production, so the method is basically not used in mass production. Compared with radiochemical method and ultraviolet irradiation method, the corona discharge method is more economic, and has the advantages of high ozone yield and low energy consumption. However, this method also has some disadvantages: high cost, easily generating carcinogenic nitrogen oxides, low ozone concentration and the like.
Since the radiochemical method and the ultraviolet irradiation method are not suitable for industrial production, but the corona discharge method widely used at present has a considerable disadvantage, researchers have proposed a method for generating ozone by an electrolytic method. The method for producing ozone by using electrolysis has the advantages of low requirement on equipment, simple equipment, convenience in movement, contribution to field preparation in different places, low investment cost, easiness in operation, high concentration of produced ozone although the quantity of the produced ozone is not large, environmental friendliness and no pollution, and can overcome the defect of a corona discharge method.
In the electrolytic process, ozone is generated by electrolysis of water. At present, the research of preparing ozone by electrochemical methods at home and abroad mainly focuses on the selection of electrode materials, particularly anode materials, such as Pd, Au and PbO2The materials are all used in the research of anode materials for preparing ozone by an electrochemical method. In the formed industrial products, lead dioxide with higher oxygen evolution potential and lower price is generally selected as the anode material.
Lead dioxide has two crystal forms of alpha and beta, beta-lead dioxide is a tetragonal crystal form, the crystal is fine, the polycrystalline structure is compact, and the oxygen evolution overpotential is high. The alpha-lead dioxide is orthorhombic, coarse in crystallization and poor in compactness. In the process of preparing ozone by electrolyzing water, the beta crystal form lead dioxide anode catalyst is obviously superior to the alpha crystal form in the aspects of ozone current efficiency and chemical stability.
At present, no experimental research work is carried out to explore the reason that the beta-lead dioxide has excellent performance for preparing ozone by electrolyzing water, so that how to prepare the beta-lead dioxide with different shapes and further obtain the influence of different crystals on the performance of the beta-lead dioxide is very significant.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide the beta-lead dioxide catalyst with different morphologies as well as the preparation method and the application thereof.
The preparation method of the beta-lead dioxide catalyst with different morphologies is characterized by comprising the following steps:
1) dissolving lead salt in deionized water, adding inorganic base, and continuously stirring for 30-60 minutes to obtain a precursor solution which is uniformly dispersed;
2) adding a structure inducer into the precursor solution obtained in the step 1), stirring for 1-3 minutes until the mixture is uniformly mixed, and continuously stirring and preserving the heat for 25-35 minutes in a water bath at the temperature of 45-55 ℃ to obtain a mixed solution;
3) adding a sodium hypochlorite solution into the mixed solution obtained in the step 2), wherein the mixed solution becomes turbid brown, and stirring for 1-3 minutes to uniformly disperse the turbid brown to obtain a suspension;
4) transferring the suspension obtained in the step 3) into a polytetrafluoroethylene tank, carrying out hydrothermal reaction at the temperature of 85-140 ℃ for 6-12 hours, and cooling to room temperature after the reaction is finished; washing the product with absolute ethyl alcohol and deionized water for 3-5 times respectively, performing suction filtration to obtain beta-lead dioxide precipitate, placing the filter residue in a vacuum drying oven, and drying at 60 ℃ for 20 hours to obtain a solid;
5) and (3) placing the solid dried in the step 4) into a plasma reaction furnace, wherein the plasma voltage is 100W-300W, the reaction temperature is 30-200 ℃, introducing high-purity gas under the vacuum-pumping condition to form a plasma atmosphere, the vacuum degree is 30Pa-100Pa, and activating for 0.2-2 hours under the plasma atmosphere to obtain the beta-lead dioxide catalyst.
The preparation method of the beta-lead dioxide catalyst with different morphologies is characterized in that the lead salt in the step 1) is lead acetate, lead nitrate, lead chloride or lead bromide; the inorganic alkali is 1M sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution or 30 wt% ammonia water; the inorganic base is added until the pH value of the precursor solution is 12-14.
The preparation method of the beta-lead dioxide catalyst with different shapes is characterized in that the structure inducers in the step 2) are Cetyl Trimethyl Ammonium Bromide (CTAB), Polyvinylpyrrolidone (PVP), Polyethylene glycol (PEG), polyoxyethylene polyoxypropylene ether block copolymer (F127, Poloxamer), the molar ratio of the addition amount of the structure inducers to the feeding of lead salt is 0.9-1.1:1, preferably 1: 1.
the preparation method of the beta-lead dioxide catalysts with different morphologies is characterized in that in the step 3), the effective chlorine concentration of the sodium hypochlorite solution is 4 wt%; the molar ratio of the available chlorine to the lead salt in the sodium hypochlorite solution is 1-6:1, preferably 1.5: 1.
The preparation method of the beta-lead dioxide catalysts with different morphologies is characterized in that the hydrothermal reaction temperature in the step 4) is 120 ℃, and the reaction time is 12 hours.
The preparation method of the beta-lead dioxide catalyst with different morphologies is characterized in that the plasma voltage in the step 5) is 150-200W; the reaction temperature is 60-100 ℃.
The preparation method of the beta-lead dioxide catalyst with different morphologies is characterized in that in the step 5), the high-purity gas is hydrogen, argon or nitrogen with the purity of more than 99%.
The preparation method of the beta-lead dioxide catalyst with different morphologies is characterized in that the vacuum degree in the step 5) is 50Pa-70 Pa; the activation time is 0.3-1 hour.
The beta-lead dioxide catalysts with different morphologies are prepared by the method.
The application of the beta-lead dioxide catalysts with different morphologies in the reaction of preparing ozone by electrocatalytic decomposition of water specifically comprises the following steps: controlling the reaction current to be 100mA-500mA by a constant current instrument, adopting an H-shaped electrolytic tank to carry out reaction, keeping water and gas smooth between two electrode chambers, taking saturated potassium sulfate aqueous solution as electrolyte, respectively coating the beta-lead dioxide catalysts with different shapes on carbon cloth as working electrodes in an anode chamber, taking a platinum sheet as a counter electrode in a cathode chamber, and controlling the tank voltage to be 5V-10V to carry out electrocatalytic reaction to obtain an ozone product.
The invention provides a method for preparing beta-lead dioxide catalysts with different shapes, aiming at the problems that commercial beta-lead dioxide is large particles, the specific surface of activity is small, and the ozone production efficiency of the commercial beta-lead dioxide is limited, the lead dioxide with different shapes and different lead dioxide with different shapes can be prepared by controlling the hydrothermal temperature and time (the catalyst obtained by the invention has uniform granular, rod-shaped, cubic and the like), the specific surface areas are different, and the exposure conditions of active sites are different, so the beta-lead dioxide catalysts are used as catalysts for preparing ozone by electrolyzing water, the activity of the beta-lead dioxide catalysts is different, and compared with the prior art, the method has the following beneficial effects:
1) the beta-lead dioxide catalysts with different morphologies are synthesized by a simple method, and in the preparation process of the catalyst, with the rise of the hydrothermal reaction temperature, the morphology of the beta-lead dioxide generated by the reaction at about 85 ℃ is a particle with the particle size of 200-500 nm; the shape of the beta-lead dioxide generated by the reaction at about 90 ℃ gradually shows a rod-shaped structure, and the length-diameter ratio is about 5:1, about 100nm in length; when the temperature rises to about 100 ℃, the integral shape of the beta-lead dioxide generated by the reaction is rod-shaped, the length-diameter ratio is about 5:1, the length is about 200-300nm, the beta-lead dioxide generated at about 120 ℃ is uniform granular, the grain diameter is about 500nm-1 mu m, and the catalyst presents a uniform cubic shape along with the rise of the reaction temperature to about 140 ℃; in the preparation process of the beta-lead dioxide catalyst, the effect of regulating the morphology of catalyst particles is achieved by regulating and controlling the temperature and time of hydrothermal reaction and the dosage of a structure inducer;
2) the beta-lead dioxide catalyst with different shapes has better stability in the reaction of preparing ozone by catalyzing electrolyzed water, and the catalytic activity is not obviously reduced after long-time electrification work;
3) the electrocatalysis process uses deionized water as electrolyte, so the cost is lower, the electrolysis process is green and pollution-free, and the electrocatalysis process is easy to control and is suitable for popularization and application.
Drawings
FIG. 1a is a schematic drawing of a scanning electron microscope at 1 μm of the particulate beta-lead dioxide obtained in example 1;
FIG. 1b is a schematic transmission electron microscope of the granular beta-lead dioxide obtained in example 1 at 0.5 μm;
FIG. 2a is a schematic drawing of a scanning electron microscope at 300nm of the rod-shaped beta-lead dioxide obtained in example 2;
FIG. 2b is a schematic transmission electron microscope of the rod-shaped beta-lead dioxide obtained in example 2 at 50 nm;
FIG. 3a is a schematic drawing of a scanning electron microscope at 200nm of the rod-shaped beta-lead dioxide obtained in example 3;
FIG. 3b is a schematic transmission electron microscope of the rod-shaped beta-lead dioxide obtained in example 3 at 100 nm;
FIG. 4a is a scanning electron microscope representation of the granular beta-lead dioxide obtained in example 4 at 2 μm;
FIG. 4b is a schematic transmission electron microscope of the granular beta-lead dioxide obtained in example 4 at 0.2 μm;
FIG. 5a is a schematic drawing of a scanning electron microscope at 2 μm of cubic lead beta dioxide obtained in example 5;
FIG. 5b is a schematic representation of a transmission electron microscope at 1 μm of cubic lead beta dioxide obtained in example 5;
FIG. 6 is a comparison graph of data obtained from real-time detection of ozone concentration when the beta-lead dioxide catalysts with different morphologies prepared in examples 1 to 5 are used for preparing ozone by electrocatalysis.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1: the preparation method of the spherical granular beta-lead dioxide catalyst comprises the following steps:
1) adding 1.5g of lead acetate and 60mL of deionized water into a beaker, performing ultrasonic treatment for 10 minutes, and stirring for 30 minutes to form a uniform solution;
2) adding 0.4g of sodium hydroxide into the solution obtained in the step 1), and continuously stirring and dispersing for 45 minutes to obtain a precursor solution;
3) adding 1.44g of CTAB powder into the precursor solution obtained in the step 2), stirring for 1-3 minutes to make the mixed solution uniform, and continuing stirring for 30 minutes in a water bath at 50 ℃;
4) adding 10mL of sodium hypochlorite solution (the effective chlorine concentration of the sodium hypochlorite solution is 4%) into the precursor solution obtained in the step 3), generating a brown-red turbid liquid, and stirring for 1-3 minutes to uniformly disperse the brown-red turbid liquid, so as to obtain a turbid liquid;
5) transferring the suspension obtained in the step 4) into a polytetrafluoroethylene tank, carrying out hydrothermal reaction at 85 ℃ for 6 hours, cooling to room temperature after the reaction is finished, and filtering to obtain a crude product;
6) washing the crude product obtained in the step 5) with absolute ethyl alcohol and deionized water for 4 times respectively, performing suction filtration, and drying filter residues in a vacuum drying oven at the temperature of 60 ℃ for 20 hours;
7) and (3) placing the dried product obtained in the step 6) into a plasma reaction furnace, wherein the plasma voltage is 200W, the reaction temperature is 80 ℃, high-purity argon is introduced under the vacuumizing condition to form a plasma atmosphere, the vacuum degree is 50Pa, and the composite catalyst is activated for 1 hour under the plasma atmosphere to obtain the beta-lead dioxide catalyst.
The schematic scanning electron microscope and the schematic transmission electron microscope at 1 μm and 0.5 μm of the beta-lead dioxide catalyst obtained in example 1 are shown in FIG. 1a and FIG. 1b, respectively, and it can be seen from FIG. 1a and FIG. 1b that the beta-lead dioxide catalyst particles are spherical particles with a size of about 200-500 nm.
The spherical granular beta-lead dioxide catalyst of example 1 was used in an experiment for preparing ozone by electrolyzing water:
weighing 8mg of the prepared granular beta-lead dioxide catalyst, respectively adding 900 mu L of ethanol and 100 mu L of Nafion solution (the mass concentration of the Nafion solution is 5%), performing ultrasonic treatment for 0.5 hour, and completely dispersing the catalyst in the mixed solution of ethanol and Nafion, thereby obtaining uniform catalyst slurry.
Cutting the carbon cloth with the specification of 2cm multiplied by 2cm, uniformly dripping the dispersed catalyst slurry on the carbon cloth, and drying to be used as a working electrode (namely, the granular beta-lead dioxide catalyst is coated on the carbon cloth to be used as the working electrode).
The voltage and current are controlled by a constant current instrument, and an H-shaped electrolytic bath is adopted for reaction. In the anode chamber, beta-lead dioxide catalysts with different shapes are coated on carbon cloth to be used as working electrodes; in the cathode chamber, a platinum sheet is used as a counter electrode, and the electrolyte is saturated potassium sulfate aqueous solution. One end of the H-shaped electrolytic cell is connected with an ozone detector to detect the generation condition of ozone in real time. When the electro-catalysis is used for preparing ozone, the current is controlled to be 200mA, the cell voltage is controlled to be 2-10V, and the reaction time is 3.5 hours. The concentration of ozone produced by the electrocatalytic reaction as the reaction proceeded is shown in figure 6. As can be seen from FIG. 6, the ozone concentration gradually increased with the progress of the reaction, and the ozone concentration reached 2463ppb when the reaction time reached 2 hours.
In order to verify the catalytic stability of the β -lead dioxide catalyst prepared in example 1, the anode chamber working electrode after 1 reaction was left to stand for 24 hours, and then an experiment for repeated electrocatalytic ozone preparation reaction was performed (the anode chamber working electrode was left to stand for one day after each use and then used again). In the 1 st experiment of the repeated utilization of the anode chamber working electrode, the ozone concentration can reach 2447ppb after 3 hours of reaction; in the 2 nd experiment, the ozone concentration can reach 2420ppb after 3 hours of reaction; in the 3 rd experiment of repeated use, the ozone concentration reached 2407ppb after 3 hours of reaction. Therefore, in the process of recycling the working electrode of the anode chamber, the electrocatalysis effect is basically not weakened, and the granular beta-lead dioxide catalyst prepared in the example 1 has better stability.
Example 2: preparing a rod-shaped beta-lead dioxide catalyst, comprising the following steps:
1) adding 1.3g of lead nitrate and 20mL of deionized water into a beaker, performing ultrasonic treatment for 10 minutes, and stirring for 30 minutes to form a uniform solution;
2) adding 30mL of ammonia water (with the concentration of 28% -30%) into the solution obtained in the step 1), and continuously stirring and dispersing for 45 minutes to obtain a precursor solution;
3) adding 250mg of PVP into the precursor solution obtained in the step 2), stirring for 1-3 minutes to ensure that the mixed solution is uniform, and continuously stirring for 30 minutes in water bath at 50 DEG C
4) Adding 10mL of sodium hypochlorite solution (the effective chlorine concentration of the sodium hypochlorite solution is 4%) into the precursor solution obtained in the step 3), generating a brown-red turbid liquid, and stirring for 1-3 minutes to uniformly disperse the brown-red turbid liquid, so as to obtain a turbid liquid;
5) transferring the suspension obtained in the step 4) into a polytetrafluoroethylene tank, carrying out hydrothermal reaction at the temperature of 90 ℃ for 6 hours, cooling to room temperature after the reaction is finished, and filtering to obtain a crude product;
6) washing the crude product obtained in the step 5) with absolute ethyl alcohol and deionized water for 4 times respectively, performing suction filtration, and drying filter residues in a vacuum drying oven at the temperature of 60 ℃ for 20 hours;
7) and (3) placing the dried product obtained in the step 6) into a plasma reaction furnace, wherein the plasma voltage is 100W, the reaction temperature is 200 ℃, high-purity argon is introduced under the vacuumizing condition to form a plasma atmosphere, the vacuum degree is 100Pa, and the composite catalyst is activated for 0.5 hour under the plasma atmosphere to obtain the beta-lead dioxide catalyst.
A scanning electron microscope diagram and a 50nm transmission electron microscope diagram of the beta-lead dioxide catalyst obtained in example 2 at 300nm are respectively shown in fig. 2a and fig. 2b, and it can be seen from fig. 2a and fig. 2b that the beta-lead dioxide catalyst particles have a rod shape, and the aspect ratio is about 5:1, about 100nm in length.
The rod-shaped beta-lead dioxide catalyst of example 2 was used in an experiment for preparing ozone by electrolyzing water:
in the case where the catalyst prepared in example 1 was used in the preparation of an electrode anode, the catalyst of example 1 added was replaced with the catalyst of example 2 of the same quality, and the remaining operating conditions were the same as those in the case of the preparation of ozone by electrolysis of water in example 1, and the concentration of ozone generated by the catalytic reaction of electrolysis of water as a function of reaction time was shown in FIG. 6. As can be seen from FIG. 6, the ozone concentration gradually increased with the progress of the reaction, and the ozone concentration reached 3073ppb for 2 hours and 3785ppb for 3 hours.
Example 3: preparing a rod-shaped beta-lead dioxide catalyst, comprising the following steps:
1) adding 1.1g of lead chloride and 50mL of deionized water into a beaker, performing ultrasonic treatment for 10 minutes, and stirring for 30 minutes to form a uniform solution;
2) adding 0.4g of sodium hydroxide into the solution obtained in the step 1), and continuously stirring and dispersing for 45 minutes to obtain a precursor solution;
3) adding 50mg of PEG into the precursor solution obtained in the step 2), stirring for 1-3 minutes to ensure that the mixed solution is uniform, and continuously stirring for 30 minutes in water bath at 50 DEG C
4) Adding 10mL of sodium hypochlorite solution (the effective chlorine concentration of the sodium hypochlorite solution is 4%) into the precursor solution obtained in the step 3), generating a brown-red turbid liquid, and stirring for 1-3 minutes to uniformly disperse the brown-red turbid liquid, so as to obtain a turbid liquid;
5) transferring the suspension obtained in the step 4) into a polytetrafluoroethylene tank, carrying out hydrothermal reaction at the temperature of 100 ℃ for 12 hours, cooling to room temperature after the reaction is finished, and filtering to obtain a rod-shaped beta-lead dioxide precipitate;
6) washing the rod-shaped beta-lead dioxide precipitate obtained in the step 5) with absolute ethyl alcohol and deionized water for 4 times respectively, performing suction filtration, and drying filter residues in a vacuum drying oven at the temperature of 60 ℃ for 20 hours;
7) and (3) placing the dried product obtained in the step 6) into a plasma reaction furnace, wherein the plasma voltage is 300W, the reaction temperature is 30 ℃, high-purity argon is introduced under the vacuum-pumping condition to form a plasma atmosphere, the vacuum degree is 30Pa, and the composite catalyst is activated for 1 hour under the plasma atmosphere to obtain the beta-lead dioxide catalyst.
A schematic scanning electron microscope and a schematic transmission electron microscope at 200nm of the β -lead dioxide catalyst obtained in example 3 are shown in fig. 3a and 3b, respectively, and it can be seen from fig. 3a and 3b that the β -lead dioxide catalyst particles have a rod shape, and the aspect ratio is about 5:1, about 200nm in length.
The rod-shaped beta-lead dioxide catalyst of example 3 was used in an experiment for the electrolysis of water to produce ozone:
in the case where the catalyst prepared in example 1 was used in the preparation of an electrode anode, the catalyst of example 1 added was replaced with the catalyst of example 3 of the same quality, and the remaining operating conditions were the same as those in the case of the preparation of ozone by electrolysis of water in example 1, and the concentration of ozone generated by the catalytic reaction of electrolysis of water as a function of reaction time was shown in FIG. 6. As can be seen from FIG. 6, the ozone concentration gradually increased with the progress of the reaction, and the ozone concentration reached 2815ppb when the reaction time reached 2 hours, and 3711ppb when the reaction time reached 3 hours.
Example 4: the preparation of the granular beta-lead dioxide catalyst comprises the following steps:
1) adding 1.5g of lead chloride and 20mL of deionized water into a beaker, performing ultrasonic treatment for 10 minutes, and stirring for 30 minutes to form a uniform solution;
2) adding 30mL of ammonia water (with the concentration of 28% -30%) into the solution obtained in the step 1), and continuously stirring and dispersing for 45 minutes to obtain a precursor solution;
3) adding 1.44g CTAB powder into the precursor solution obtained in the step 2), stirring for 1-3 minutes to make the mixed solution uniform, and continuing stirring in a water bath at 50 ℃ for 30 minutes
4) Adding 10mL of sodium hypochlorite solution (the effective chlorine concentration of the sodium hypochlorite solution is 4%) into the precursor solution obtained in the step 3), generating a brown-red turbid liquid, and stirring for 1-3 minutes to uniformly disperse the brown-red turbid liquid, so as to obtain a turbid liquid;
5) transferring the suspension obtained in the step 4) into a polytetrafluoroethylene tank, carrying out hydrothermal reaction at 120 ℃ for 12 hours, cooling to room temperature after the reaction is finished, and filtering to obtain granular beta-lead dioxide precipitate;
6) washing the granular beta-lead dioxide precipitate obtained in the step 5) with absolute ethyl alcohol and deionized water for 4 times respectively, performing suction filtration, and drying filter residues in a vacuum drying oven at the temperature of 60 ℃ for 20 hours;
7) and (3) placing the dried product obtained in the step 6) into a plasma reaction furnace, wherein the plasma voltage is 300W, the reaction temperature is 150 ℃, high-purity argon is introduced under the vacuumizing condition to form a plasma atmosphere, the vacuum degree is 100Pa, and the composite catalyst is activated for 1 hour under the plasma atmosphere to obtain the beta-lead dioxide catalyst.
The scanning electron microscope and the 0.2 μm transmission electron microscope of the granular beta-lead dioxide catalyst obtained in example 4 at 2 μm are shown in fig. 4a and 4b, respectively, and it can be seen from fig. 4a and 4b that the beta-lead dioxide catalyst is granular with a grain size of 1 to 2 μm.
The granular beta-lead dioxide catalyst of example 4 was used in an experiment for the electrolysis of water to produce ozone:
in the case where the catalyst prepared in example 1 was used in the preparation of an electrode anode, the catalyst of example 1 added was replaced with the catalyst of example 4 of the same quality, and the remaining operating conditions were the same as those in the case of the preparation of ozone by electrolysis of water in example 1, and the concentration of ozone generated by the catalytic reaction of electrolysis of water as a function of reaction time was shown in FIG. 6. As can be seen from FIG. 6, the ozone concentration gradually increased with the progress of the reaction, and the ozone concentration reached 3719ppb when the reaction time reached 2 hours, and 4038ppb when the reaction time reached 3 hours.
Example 5: preparing a cubic beta-lead dioxide catalyst comprising the steps of:
1) adding 1.3g of lead chloride and 20mL of deionized water into a beaker, performing ultrasonic treatment for 10 minutes, and stirring for 30 minutes to form a uniform solution;
2) adding 1.3g of potassium hydroxide into the solution obtained in the step 1), and continuously stirring and dispersing for 45 minutes to obtain a precursor solution;
3) adding 100mg CTAB powder into the precursor solution obtained in the step 2), stirring for 1-3 minutes to ensure that the mixed solution is uniform, and continuously stirring for 30 minutes in water bath at 50 ℃;
4) adding 10mL of sodium hypochlorite solution (the effective chlorine concentration of the sodium hypochlorite solution is 4%) into the precursor solution obtained in the step 3), generating a brown-red turbid liquid, and stirring for 1-3 minutes to uniformly disperse the brown-red turbid liquid, so as to obtain a turbid liquid;
5) transferring the suspension obtained in the step 4) into a polytetrafluoroethylene tank, carrying out hydrothermal reaction at the temperature of 140 ℃ for 6 hours, cooling to room temperature after the reaction is finished, and filtering to obtain a cubic beta-lead dioxide precipitate;
6) washing the cubic beta-lead dioxide precipitate obtained in the step 5) with absolute ethyl alcohol and deionized water for 4 times respectively, performing suction filtration, and drying filter residues in a vacuum drying oven at the temperature of 60 ℃ for 20 hours;
7) and (3) placing the dried product obtained in the step 6) into a plasma reaction furnace, wherein the plasma voltage is 300W, the reaction temperature is 150 ℃, high-purity argon is introduced under the vacuumizing condition to form a plasma atmosphere, the vacuum degree is 100Pa, and the composite catalyst is activated for 1 hour under the plasma atmosphere to obtain the beta-lead dioxide catalyst.
The scanning electron microscope and the transmission electron microscope at 2 μm and 0.2 μm of the beta-lead dioxide catalyst obtained in example 4 are schematically illustrated in fig. 5a and 5b, respectively, and it can be seen from fig. 5a and 5b that the beta-lead dioxide catalyst is cubic with a side of about 1 to 2 μm.
The cubic beta-lead dioxide catalyst of example 5 was used in an experiment for the electrolysis of water to produce ozone:
in the case where the catalyst prepared in example 1 was used in the preparation of an electrode anode, the catalyst of example 1 added was replaced with the catalyst of example 5 of the same quality, and the remaining operating conditions were the same as those in the case of the preparation of ozone by electrolysis of water in example 1, and the concentration of ozone generated by the catalytic reaction of electrolysis of water as a function of reaction time was shown in FIG. 6. As can be seen from FIG. 6, as the reaction proceeds, the ozone concentration gradually increases, and the ozone concentration can reach 3137ppb when the reaction time reaches 2 hours, and 3898ppb when the reaction time reaches 3 hours.
Comparative example 6: commercial lead dioxide of over 97% purity, available from mcelin reagent net, was applied to the electrolyzed water ozone production experiments:
weighing 8mg of commercial lead dioxide catalyst, respectively adding 900 mu L of ethanol and 100 mu L of Nafion solution (the mass concentration of the Nafion solution is 5%), and performing ultrasonic treatment for 0.5 hour to completely disperse the catalyst in the mixed solution of the ethanol and the Nafion, thereby obtaining uniform catalyst slurry.
Cutting the carbon cloth with the specification of 2cm multiplied by 2cm, uniformly dripping the dispersed catalyst slurry on the carbon cloth, and drying to be used as a working electrode.
The voltage and current are controlled by a constant current instrument, and an H-shaped electrolytic bath is adopted for reaction. In the anode chamber, beta-lead dioxide catalysts with different shapes are coated on carbon cloth to be used as working electrodes; in the cathode chamber, a platinum sheet is used as a counter electrode, and the electrolyte is saturated potassium sulfate aqueous solution. One end of the H-shaped electrolytic cell is connected with an ozone detector to detect the generation condition of ozone in real time. When the electro-catalysis is used for preparing ozone, the current is controlled to be 200mA, the cell voltage is controlled to be 2-10V, and the reaction time is 3.5 hours. The concentration of ozone produced by the electrocatalytic reaction as the reaction proceeded is shown in figure 6. As can be seen from FIG. 6, the ozone concentration gradually increased as the reaction proceeded, and reached 2200ppb after the reaction for 2 hours.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (10)
1. A preparation method of beta-lead dioxide catalysts with different morphologies is characterized by comprising the following steps:
1) dissolving lead salt in deionized water, adding inorganic base, and continuously stirring for 30-60 minutes to obtain a precursor solution which is uniformly dispersed;
2) adding a structure inducer into the precursor solution obtained in the step 1), stirring for 1-3 minutes until the mixture is uniformly mixed, and continuously stirring and preserving the heat for 25-35 minutes in a water bath at the temperature of 45-55 ℃ to obtain a mixed solution;
3) adding a sodium hypochlorite solution into the mixed solution obtained in the step 2), wherein the mixed solution becomes turbid brown, and stirring for 1-3 minutes to uniformly disperse the turbid brown to obtain a suspension;
4) transferring the suspension obtained in the step 3) into a polytetrafluoroethylene tank, carrying out hydrothermal reaction at the temperature of 85-140 ℃ for 6-12 hours, and cooling to room temperature after the reaction is finished; washing the product with absolute ethyl alcohol and deionized water for 3-5 times respectively, performing suction filtration to obtain beta-lead dioxide precipitate, placing the filter residue in a vacuum drying oven, and drying at 60 ℃ for 20 hours to obtain a solid;
5) and (3) placing the solid dried in the step 4) into a plasma reaction furnace, wherein the plasma voltage is 100W-300W, the reaction temperature is 30-200 ℃, introducing high-purity gas under the vacuum-pumping condition to form a plasma atmosphere, the vacuum degree is 30Pa-100Pa, and activating for 0.2-2 hours under the plasma atmosphere to obtain the beta-lead dioxide catalyst.
2. The method for preparing beta-lead dioxide catalysts with different morphologies according to claim 1, wherein the lead salt in the step 1) is lead acetate, lead nitrate, lead chloride or lead bromide; the inorganic alkali is 1M sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution or 30 wt% ammonia water; the inorganic base is added until the pH value of the precursor solution is 12-14.
3. The method for preparing beta-lead dioxide catalysts with different morphologies according to claim 1, wherein the structure-inducing agent in step 2) is cetyl trimethyl ammonium bromide, polyvinylpyrrolidone, polyethylene glycol or polyoxyethylene polyoxypropylene ether block copolymer, respectively, and the molar ratio of the added amount of the structure-inducing agent to the added amount of the lead salt is 0.9-1.1:1, preferably 1: 1.
4. the method for preparing beta-lead dioxide catalysts with different morphologies according to claim 1, wherein in the step 3), the effective chlorine concentration of the sodium hypochlorite solution is 4 wt%; the molar ratio of the available chlorine to the lead salt in the sodium hypochlorite solution is 1-6:1, preferably 1.5: 1.
5. The method for preparing beta-lead dioxide catalysts with different morphologies according to claim 1, wherein the hydrothermal reaction temperature in the step 4) is 120 ℃ and the reaction time is 12 hours.
6. The method for preparing beta-lead dioxide catalysts with different morphologies according to claim 1, wherein the plasma voltage in the step 5) is 150W-200W; the reaction temperature is 60-100 ℃.
7. The method for preparing beta-lead dioxide catalysts with different morphologies according to claim 1, wherein in the step 5), the high purity gas is hydrogen, argon or nitrogen with a purity of > 99%.
8. The preparation method of the beta-lead dioxide catalysts with different morphologies according to claim 1, wherein the vacuum degree in the step 5) is 50Pa to 70 Pa; the activation time is 0.3-1 hour.
9. Beta-lead dioxide catalysts of different morphologies prepared by the method of any one of claims 1 to 8.
10. Use of the different morphology beta-lead dioxide catalyst of claim 9 in electrocatalytic decomposition of water to ozone reaction.
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| CN112481643A (en) * | 2020-11-27 | 2021-03-12 | 浙江工业大学 | Lead tetroxide catalyst with different morphologies as well as preparation method and application thereof |
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