CN115448367B - Preparation method of yellow-tungstic acid catalyst and application of yellow-tungstic acid catalyst in piezocatalysis of hydrogen peroxide - Google Patents
Preparation method of yellow-tungstic acid catalyst and application of yellow-tungstic acid catalyst in piezocatalysis of hydrogen peroxide Download PDFInfo
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000003377 acid catalyst Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004299 exfoliation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000000527 sonication Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- MHWZQNGIEIYAQJ-UHFFFAOYSA-N molybdenum diselenide Chemical compound [Se]=[Mo]=[Se] MHWZQNGIEIYAQJ-UHFFFAOYSA-N 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 108091006149 Electron carriers Proteins 0.000 description 1
- -1 Transition metal chalcogenides Chemical class 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- UYLYBEXRJGPQSH-UHFFFAOYSA-N sodium;oxido(dioxo)niobium Chemical compound [Na+].[O-][Nb](=O)=O UYLYBEXRJGPQSH-UHFFFAOYSA-N 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
-
- 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
- C25B1/28—Per-compounds
- C25B1/30—Peroxides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method and application of a yellow-tungstic acid catalyst, comprising the following steps: in a commercial WS 2 As a parent, adding the compound into a nitric acid solution, and preparing the WO with (111) crystal face enhanced growth by a simple ultrasonic oxidation stripping mode 3 ·H 2 O catalyst (commonly known as Huang Wusuan). Research shows that WS with different particle sizes 2 The catalytic properties of the prepared yellow-tungstic acid are different, and the oxidation stripping time also influences the chemical structure and the catalytic properties of the yellow-tungstic acid. The target catalyst is applied to a piezoelectric catalytic hydrogen peroxide generation system, and has obviously enhanced hydrogen peroxide generation performance (the yield is 23.91 (+ -1.79) mM/h/g).
Description
Technical Field
The invention relates to the fields of nano material engineering and energy engineering, in particular to a preparation method of a yellow-tungstic acid catalyst and application of the yellow-tungstic acid catalyst in piezocatalysis of hydrogen peroxide.
Background
The mechanical energy in the nature is visible everywhere, and is also convenient and easy to obtain, such as wind energy, tidal energy and the like. The piezoelectric semiconductor is deformed by external force (mechanical force) in the environment, and a polarized piezoelectric field is generated inside the semiconductor to separate carriers to participate in oxidation-reduction reaction, so that mechanical energy is converted into chemical energy. Common piezoelectric catalysts are semiconductor and semiconductor heterojunctions, such as zinc oxide (ZnO), copper sulfide/zinc oxide (CuS/ZnO), perovskite species such as barium titanate (BaTiO) 3 ) Sodium niobate (NaNbO) 3 ) And lead zirconate titanate (Pb (Zr, ti) O) 3 ) Transition metal chalcogenides, e.g. molybdenum disulphide (MoS 2 ) Molybdenum diselenide (MoSe) 2 ). They have an asymmetric crystal structure and have enhanced catalytic properties due to the tilt of the band structure under external constraint. The Wang Zhonglin first proposed the concept of friction nano-generators (Triboelectric nanogenerator, TENG) and applied them widely for environmental energy collection, capture and conversion, piezocatalysis being one of the most common driving forces for piezocatalysis.
The hydrogen peroxide is generated by a traditional large-scale synthetic anthraquinone chemical method, mainly by oxygen and hydrogen through homogeneous proton/electron carriers. The method has obvious disadvantages including high temperature and high pressure required by the reaction, easy explosion of hydrogen and oxygen mixture and costHigh and serious secondary pollution, etc. Ultrasonic-stimulated piezoelectricity catalytic hydrogen peroxide (H) 2 O 2 ) Is an effective hydrogen peroxide obtaining mode. The semiconductor catalyst is polarized by the piezoelectric process to produce a carrier separation effect. And (3) carrying out an oxygen reduction reaction by utilizing the reduction potential of the conduction band to generate two-electron hydrogen peroxide, or carrying out water molecule oxidation by utilizing the oxidation potential of the valence band to generate four-electron hydrogen peroxide. Wherein the selection and preparation of the piezoelectric catalyst is of paramount importance.
WO 3 ·H 2 O is commonly called as yellow tungstic acid, and the most common preparation method is sodium tungstate acidification, and also comprises an ion exchange method and a solvent extraction method. It is a catalyst commonly used in organic catalytic reactions, such as the oxidation of cyclohexane to adipic acid. In the present application commercial tungsten disulfide (WS) 2 ) WO formed by stripping oxidation 3 ·H 2 The XRD characterization of O (commonly known as Huang Wusuan) shows that the (111) crystal face of the catalyst is enhanced to be generated, and the experimental result shows that the catalyst has the capability of remarkably promoting the generation of the piezoelectric catalytic hydrogen peroxide. Comparative experiments show that the parent WS 2 The particle size and the stripping oxidation time of the catalyst have an influence on the chemical structure and the catalytic performance of the target catalyst, namely the yellow-tungstic acid.
Disclosure of Invention
The invention provides a preparation method of a yellow-tungstic acid catalyst and application thereof in piezoelectricity catalysis of hydrogen peroxide generation.
A preparation method of a yellow-tungstic acid catalyst comprises the following steps:
tungsten disulfide (WS) 2 ) Placing the parent material in concentrated nitric acid, and oxidizing and stripping by ultrasonic and stirring to obtain parent material WS 2 Transformation into (111) surface enhanced growth WO 3 •H 2 O (Huang Wusuan) and obtaining the yellow-tungstic acid catalyst through post-treatment. And carrying out piezoelectric catalysis on the material in an ultrasonic mode to produce hydrogen peroxide.
The particle size of the tungsten disulfide is 80-nm mu m.
The dosage ratio of the tungsten disulfide to the concentrated nitric acid is 150-250 mg:15 to 25 mL, more preferably 200 mg:20 And (3) mL.
The mass fraction of the concentrated nitric acid is 60% -70%, and more preferably 68%.
The ultrasonic treatment time is 20-50 minutes.
The stirring time is 3-10 hours.
The post-treatment comprises centrifugation, washing and drying, wherein the washing is performed for a plurality of times by using deionized water and ethanol until the pH value of the last washing solution is close to neutral.
The prepared Huang Wusuan catalyst is subjected to piezoelectric catalysis to produce hydrogen peroxide in an ultrasonic mode, and the specific steps are as follows:
1) Dispersing Huang Wusuan catalyst in a mixed solution of deionized water and isopropanol;
2) The reaction induces hydrogen peroxide production through ultrasonic vibration provided by an ultrasonic cleaning machine, and the concentration test of the hydrogen peroxide is carried out by taking points in a set time interval. And (3) injection: the piezocatalysis reaction does not need to be exposed to any oxygen-containing gas.
In the step 1), the dosage ratio of the Huang Wusuan catalyst, deionized water and isopropanol is 15-25 mg: 14-24 mL:0.5 to 2 mL, more preferably 20 mg:19 mL:1 mL.
In step 2), the parameters of the ultrasonic machine are 110W and 37 kHz. To prevent excessive temperatures during sonication, ice cooling is used.
Compared with the prior art, the invention has the following advantages:
(1) WS to be commercialized in the present invention 2 The catalyst is stripped and modified into a yellow tungstic acid series under the action of ultrasonic stirring through a strong oxidizing environment constructed by concentrated nitric acid, and has a nano flower-like structure, compared with a parent WS 2 The specific surface area of the target catalyst is improved by more than 10 times. The method for preparing the yellow-tungstic acid is convenient and easy to obtain, and can be popularized in a large scale.
(2) The target catalyst has remarkable performance of piezoelectricity catalysis hydrogen peroxide generation, and the optimal performance of hydrogen peroxide generation is 23.91 (+ -1.79) millimoles/hour/gram, and is obtained under the condition of not exposing any oxygen-containing gas. Parent WS 2 Size and oxygen of (2)The chemical stripping time has an influence on the chemical structure and the catalytic performance of the target catalyst, namely the yellow-tungstic acid. WS (WS) 2 The smaller the particle size is, the better the performance of producing hydrogen peroxide by piezoelectric catalysis of the prepared yellow tungstic acid is. The oxidation stripping time is controlled to be 5 hours, and the prepared yellow-tungstic acid catalyst has the best hydrogen peroxide production performance.
Drawings
FIG. 1 is a scanning electron microscope image of the catalyst WSO-T prepared in example 1;
FIG. 2 shows the WSO-T, WO synthesized in example 1 and example 4 3 •H 2 O and commercialized WS 2 An XRD pattern of (b);
FIG. 3 is a graph showing adsorption and desorption curves and specific surface areas of nitrogen of the catalyst WSO-T prepared in example 1;
FIG. 4 shows WSO-T, WO synthesized in example 1 and example 4 3 ·H 2 O and commercialized WS 2 The performance diagram of the ultrasonic stimulated piezocatalysis hydrogen peroxide production;
FIG. 5 shows WS of different particle sizes in examples 1,2 and 3 2 The performance diagram of hydrogen peroxide production by piezocatalysis of the prepared WSO-5.
Description of the embodiments
The invention is further illustrated by the following examples in conjunction with the accompanying drawings.
1. The specific steps of the synthesis of the catalyst WSO-T comprise the following steps:
1) Taking a certain quality of commercial WS 2 As a master, add to a 100 mL conical flask. Commercial WS of a certain quality 2 Optimal amount after optimization is 200 mg, WS 2 The optimal value after the particle size optimization is 100 nm;
2) Slowly adding a certain volume of concentrated nitric acid solution into the conical flask, wherein the optimal value of the optimized concentrated nitric acid volume is 20 mL;
3) Placing the mixture into an ultrasonic machine for ultrasonic treatment for a period of time, wherein the power of ultrasonic treatment is 37 kHz, and the optimal value after ultrasonic treatment is 30 minutes;
4) After the ultrasonic treatment is finished, adding a certain volume of deionized water, wherein the optimal volume value of the optimized deionized water is 25 mL;
5) Stirring on a stirrer for a certain time, wherein the optimal value after the stirring time is optimized is 5 hours;
6) Centrifuging the product obtained in step 5), washing with deionized water and ethanol for several times until the final eluate pH is near neutral. The product obtained is abbreviated as WSO-T, T representing the oxidative exfoliation time.
Example 1
1) Commercial WS with particle size of 100 nm of 200 mg is taken 2 As a master, into a 100 mL conical flask;
2) Slowly adding concentrated nitric acid (mass fraction 68%) of 20 mL into the conical flask;
3) Placing the mixture in an ultrasonic machine for ultrasonic treatment for 30 min (ultrasonic power is 37 kHz), and making WS 2 Performing preliminary stripping;
4) After the ultrasound was completed, 25 mL deionized water was added and stirred on a stirrer for a period of time T, t=1, 2,3,5 and 10 hours;
5) Centrifuging the product obtained in the step 4), and washing the product with deionized water and ethanol for several times until the pH of the final washing liquid is close to neutral. The obtained product is abbreviated as WSO-T, and T represents the oxidation stripping time;
6) Drying the solid powder catalyst in the step 5) in an oven for standby, wherein the temperature of the oven is 60 DEG C o And C, the time is 4 hours.
Example 2
1) Commercial WS with particle size of 27 μm was taken 200 mg 2 As a master, into a 100 mL conical flask;
2) Slowly adding concentrated nitric acid (mass fraction 68%) of 20 mL into the conical flask;
3) Placing the above mixture in an ultrasonic machine, and ultrasonic treating for 30 min (ultrasonic power of 37 kHz) to make WS 2 Performing preliminary stripping;
4) After the ultrasonic treatment, adding 25 mL deionized water, and stirring on a stirrer for 5 hours;
5) Centrifuging the product obtained in the step 4), and washing the product with deionized water and ethanol for several times until the pH of the final washing liquid is close to neutral. The product obtained is abbreviated as WSO-5,5 represents oxidative stripping for 5 hours;
6) Drying the solid powder catalyst in the step 5) in an oven for standby, wherein the temperature of the oven is 60 DEG C o And C, the time is 4 hours.
Example 3
1) Commercial WS with particle size of 2 μm was taken 200 mg 2 As a master, into a 100 mL conical flask;
2) Slowly adding concentrated nitric acid (mass fraction 68%) of 20 mL into the conical flask;
3) Placing the mixture in an ultrasonic machine for ultrasonic treatment for 30 min (ultrasonic power is 37 kHz), and making WS 2 Performing preliminary stripping;
4) After the ultrasonic treatment, adding 25 mL deionized water, and stirring on a stirrer for 5 hours;
5) Centrifuging the product obtained in the step 4), and washing the product with deionized water and ethanol for several times until the pH of the final washing liquid is close to neutral. The product obtained is abbreviated as WSO-5,5 represents oxidative stripping for 5 hours;
6) Drying the solid powder catalyst in the step 5) in an oven for standby, wherein the temperature of the oven is 60 DEG C o And C, the time is 4 hours.
Example 4
1) 25 mL of sodium tungstate dihydrate (Na) of 0.2 mol/L 2 WO 4 ·2H 2 O) heating and stirring to 60 on a magnetic heating stirrer o C：
2) Adding 30 mL of concentrated sulfuric acid with the concentration of 6 mol/L dropwise under stirring;
3) Standing for 2 hours, WO 3 ·H 2 The O nano solid powder is gradually separated out, and is centrifugally washed for a plurality of times for standby.
4) Drying the solid powder catalyst in the step 3) in an oven for standby, wherein the temperature of the oven is 60 DEG C o And C, the time is 4 hours.
The application of preparing hydrogen peroxide by piezocatalysis specifically comprises the following steps:
the catalyst prepared in the above embodiment is selected for the piezoelectric catalytic hydrogen peroxide generation process of ultrasonic stimulation. The experimental procedure was as follows:
powdered catalyst 20, mg, was dispersed in a mixed solution of 19 mL deionized water and 1 mL isopropyl alcohol, the initial pH of the solution being 4. The reaction was induced by ultrasonic vibration provided by an ultrasonic cleaner with parameters of 110W, 37 kHz. To prevent excessive temperatures during sonication, ice cooling is used. And taking a point in a set time interval, and performing concentration test of hydrogen peroxide. And (3) injection: the piezocatalysis reaction does not need to be exposed to any oxygen-containing gas.
2. The method of the invention is used for the treatment process
1) The catalyst 20 mg prepared in the above process is taken in a mixed solution of 19 mL deionized water and 1 mL isopropanol;
2) And (3) starting the ultrasonic machine, triggering piezoelectric catalytic reaction through ultrasonic vibration provided by the ultrasonic cleaning machine, taking points in a set time interval, and testing the concentration of hydrogen peroxide generated in the system. To prevent excessive temperatures during sonication, ice cooling is used.
3. Effects obtained by this embodiment
FIG. 1 is a scanning electron microscope image of the catalyst WSO-T prepared in example 1. From FIG. 1 a), it was found that WS was commercialized 2 The process of ultrasonic stripping makes the massive WS in the form of massive hexagon structure 2 Gradually separating and disintegrating. The surface of the material shows nano flower-like growth in a strong oxidizing environment. As the oxidation time increases, the blocks become smaller and the petals of the surface nanoflower become sharper. FIG. 1 b-e) corresponds in turn to the scanning electron microscope images of samples prepared in example 1 with oxidation time ratios of 1, 3,5 and 10 hours. It is clear from the internal graph that the edge thickness becomes thinner as the oxidation time increases.
FIG. 2 shows the WSO-T, WO synthesized in example 1 and example 4 3 •H 2 O and commercialized WS 2 Is a XRD pattern of (C). FIG. 2 a) it can be seen that the commercial WS 2 A strong diffraction peak was exhibited at the (002) plane position. Indicating that the crystallinity is very good. The catalyst prepared in example 4 is typically WO 3 •H 2 O, its JCDF card number is 84-0886. However, according to the embodimentThe WSO-5 prepared in 1 showed the same XRD pattern as the catalyst prepared in example 4, indicating that WSO-5 is a yellow tungstic acid. In contrast, the (111) plane in WSO-5 is enhanced in growth. FIG. 2 b) is an XRD pattern of a WSO-T sample at different oxidation times. Interestingly, parent WS with relatively short oxidative exfoliation times, such as WSO-1 and WSO-2 2 The (002) plane of (b) is still preserved. WS with oxidative stripping time exceeding 3 hours 2 The peak of (002) face in (a) completely disappeared, and pure WO was obtained 3 •H 2 O. For the sake of expression accuracy, we expressed the sample prepared in example 1 as WSO-T.
FIG. 3 is a graph showing the adsorption and desorption curves and specific surface areas of nitrogen of the catalyst WSO-T prepared in example 1. From the adsorption and desorption curve of the catalyst to nitrogen, the micropores and mesopores of the catalyst are few and almost none. At relatively high pressures (> 0.5), hysteresis loops appear, indicating the presence of a macroporous structure in the catalyst. This suggests that the strongly oxidizing environment promotes vacancy in the bulk material. Their specific surface areas were obtained according to the BET calculation method, as shown in FIG. 3b. The specific surface area of the catalyst gradually increased as the oxidative exfoliation proceeded, from 3.33 to m of the precursor 2 /g increased to a maximum of 39.4. 39.4 m 2 Per g (WSO-10), by more than a factor of 10.
FIG. 4 is a graph comparing the catalytic production of hydrogen peroxide under different systems. As shown in FIG. 4a, a commercial WS 2 The WSO-5 has remarkable hydrogen peroxide generating performance, and the yield of the reaction reaches 478.12 (+ -25.33) mu m in 1 hour. It is worth mentioning that the excellent hydrogen peroxide generating performance is achieved by only utilizing natural solution oxygen in the system without exposing any oxygen-containing gas. When the external vibration condition is removed, the WSO-5 catalyst shows the property of hardly generating hydrogen peroxide. This suggests that the excellent hydrogen peroxide generating capacity of WSO-5 results from the piezocatalysis process. In contrast, WO synthesized by liquid phase deposition in example 4 3 ·H 2 O performs the preparation of piezoelectrically catalyzed hydrogen peroxide and also shows negligible yield. The results demonstrate the (111) plane enhancement in example 1WSO-5 exhibits excellent hydrogen peroxide piezocatalysis generation capability, and is not common to yellow-tungstic acid. FIG. 4b is an ultraviolet-visible absorption curve of the POD/DPD method for detecting the generation of hydrogen peroxide by WSO-5.
We explore the hydrogen peroxide production performance of WSO-T series catalysts, see FIG. 4c. As the oxidation time increases, WSO-T exhibits enhanced hydrogen peroxide formation. The hydrogen peroxide generating performance of the catalyst WSO-1 is the weakest, the WSO-5 reaches the optimal value, and the WSO-10 is reduced. Therefore, the WSO-5 catalyst was the best performing catalyst, and the oxidation stripping time of the catalysts prepared in examples 2 and 3 was 5 hours. FIG. 4d shows the yield of WSO-T to hydrogen peroxide, with the highest yield of WSO-5 being 23.91 (+ -1.79) mM/h/g.
FIG. 5 is a sample of WS of different particle sizes from examples 1,2 and 3 2 (figure 5 a) shows the performance diagram of piezocatalysis hydrogen peroxide production of the WSO-5. According to experimental results, WS with different particle sizes 2 WSO-5 prepared from the parent body has influence on the performance of hydrogen peroxide production by piezocatalysis. 100 nm-sized parent WS 2 The prepared WSO-5 has the best hydrogen peroxide generating performance, and WS of 27 mu m 2 The prepared WSO-5 has the worst performance in producing hydrogen peroxide through piezoelectric catalysis. WS of smaller particle size 2 The edge nanometer petals of WSO-5 prepared by the parent are thinner. It is more favorable for the full contact of the three-phase interface and the catalytic reaction in the electron transmission.
Claims (4)
1. The preparation method of the yellow-tungstic acid catalyst is characterized by comprising the following steps of:
tungsten disulfide is taken as a parent body and is placed in concentrated nitric acid, oxidation stripping is carried out through ultrasonic and stirring, and a yellow tungstic acid catalyst is obtained through post-treatment, wherein the Huang Wusuan catalyst has a nano flower-shaped structure;
the particle size of the tungsten disulfide is 80 nm-2 mu m;
the mass fraction of the concentrated nitric acid is 60% -70%;
the dosage ratio of the tungsten disulfide to the concentrated nitric acid is 150-250 mg: 15-25 mL;
the ultrasonic treatment time is 20-50 minutes;
the stirring time is 3-5 hours.
2. The method of claim 1, wherein the post-treatment comprises centrifugation, washing and drying, the washing being performed several times with deionized water and ethanol until the final wash pH is near neutral.
3. Use of the Huang Wusuan catalyst prepared by the method according to claim 1 or 2 in piezocatalysis to produce hydrogen peroxide, comprising:
1) Dispersing Huang Wusuan catalyst in a mixed solution of deionized water and isopropanol;
2) The reaction induces hydrogen peroxide production through ultrasonic vibration provided by an ultrasonic cleaner.
4. The use according to claim 3, wherein in step 1), the ratio of the amounts of Huang Wusuan catalyst, deionized water and isopropyl alcohol is 15-25 mg: 14-24 mL: 0.5-2 mL.
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| CN106824190A (en) * | 2017-03-03 | 2017-06-13 | 中国科学技术大学先进技术研究院 | A kind of WO3‑xNanocatalyst and its preparation, application |
| KR101800811B1 (en) * | 2017-03-16 | 2017-11-24 | 신정민 | Method for manufacturing tungsten oxide and tungsten oxide manufactured by the same |
| CN109174128A (en) * | 2018-09-13 | 2019-01-11 | 浙江大学 | A kind of method of modifying of tungsten disulfide and its application |
| CN114105203A (en) * | 2021-11-08 | 2022-03-01 | 昆明理工大学 | C-WO applied to two-electron oxygen reduction reaction3Nano material and preparation method thereof |
| CN114180630A (en) * | 2021-12-27 | 2022-03-15 | 南京理工大学 | Multilayer nano plate-shaped WO3 and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106824190A (en) * | 2017-03-03 | 2017-06-13 | 中国科学技术大学先进技术研究院 | A kind of WO3‑xNanocatalyst and its preparation, application |
| KR101800811B1 (en) * | 2017-03-16 | 2017-11-24 | 신정민 | Method for manufacturing tungsten oxide and tungsten oxide manufactured by the same |
| CN109174128A (en) * | 2018-09-13 | 2019-01-11 | 浙江大学 | A kind of method of modifying of tungsten disulfide and its application |
| CN114105203A (en) * | 2021-11-08 | 2022-03-01 | 昆明理工大学 | C-WO applied to two-electron oxygen reduction reaction3Nano material and preparation method thereof |
| CN114180630A (en) * | 2021-12-27 | 2022-03-15 | 南京理工大学 | Multilayer nano plate-shaped WO3 and preparation method and application thereof |
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