CN115448367A - Preparation method of fulvic acid catalyst and application of fulvic acid catalyst in piezoelectric catalytic hydrogen peroxide - Google Patents

Preparation method of fulvic acid catalyst and application of fulvic acid catalyst in piezoelectric catalytic hydrogen peroxide Download PDF

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CN115448367A
CN115448367A CN202211055634.8A CN202211055634A CN115448367A CN 115448367 A CN115448367 A CN 115448367A CN 202211055634 A CN202211055634 A CN 202211055634A CN 115448367 A CN115448367 A CN 115448367A
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acid catalyst
hydrogen peroxide
fulvic acid
catalyst
ultrasonic
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CN115448367B (en
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王娟
左四进
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Zhejiang University ZJU
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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Abstract

The invention discloses a preparation method and application of a fulvic acid catalyst, which comprises the following steps: in commercial WS 2 Adding the precursor into a nitric acid solution, and preparing the WO with the (111) crystal face enhanced growth by a simple ultrasonic oxidation stripping mode 3 ·H 2 O catalyst (commonly known as yellow tungstic acid). WS of different particle sizes 2 The catalytic performance of the prepared tungstic acid is different, and the chemical structure and the catalytic performance of the tungstic acid are influenced by the oxidation stripping time. The target catalyst is applied to a generation system of the piezoelectric catalytic hydrogen peroxide, and has remarkably enhanced hydrogen peroxide generation performance (the yield is 23.91 (+/-1.79) m mu/h/g).

Description

Preparation method of fulvic acid catalyst and application of fulvic acid catalyst in piezoelectric catalytic hydrogen peroxide
Technical Field
The invention relates to the field of nano material engineering and energy engineering, in particular to a preparation method of a fulvic acid catalyst and application of the fulvic acid catalyst in piezoelectric catalytic hydrogen peroxide.
Background
The mechanical energy of the nature can be seen everywhere, and is 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 in the semiconductor to separate carriers to participate in an oxidation-reduction reaction, so that mechanical energy is converted into chemical energy. Common piezoelectric catalysts are semiconductors and semiconductor heterojunctions, such as zinc oxide (ZnO), copper sulfide/oxideZinc (CuS/ZnO), perovskites 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 disulfide (MoS) 2 ) Molybdenum diselenide (MoSe) 2 ). They have asymmetric crystal structures with enhanced catalytic performance due to band structure tilt under external constraint forces. Mr. Wangzhong originally proposed the concept of a Triboelectric nanogenerator (TENG) and widely applied to the collection, capture and conversion of environmental energy sources, piezoelectric catalytic reaction is one of them, and ultrasonic stimulation is one of the most common driving forces of piezoelectric catalytic reaction.
The hydrogen peroxide has important application in various aspects of human production and life and the like. It is a strong oxidant, and can be directly used for sterilization and disinfection of drinking water, degradation and mineralization of organic pollutants in water body and even treatment of new coronary pneumonia (COVID-19) virus under the condition of lower concentration. The product is green and does not need secondary treatment. The hydrogen peroxide is generated by a traditional large-scale synthetic anthraquinone chemical method, and mainly by using oxygen and hydrogen through a homogeneous proton/electron carrier. The method has obvious disadvantages including high temperature and high pressure required by the reaction, easy explosion of hydrogen and oxygen mixture, high cost, serious secondary pollution and the like. Piezoelectric catalytic hydrogen peroxide (H) stimulated by ultrasonic wave 2 O 2 ) The method is an effective hydrogen peroxide acquisition mode. The polarization of the semiconductor catalyst by the piezoelectric process produces a carrier separation effect. The process of generating the two-electron hydrogen peroxide by using the reduction potential of the conduction band to perform oxygen reduction reaction or the process of generating the four-electron hydrogen peroxide by using the oxidation potential of the valence band to perform water molecule oxidation. Wherein the selection and preparation of the piezoelectric catalyst is crucial.
WO 3 ·H 2 The most common preparation method of O is acidification by sodium tungstate hydrochloric acid, and an ion exchange method and a solvent extraction method are also used. It is a catalyst commonly used in organic catalytic reactions, such as the oxidation of cyclohexane to adipic acid. Commercial tungsten disulfide (WS) is used in this application 2 ) Stripping oxidized WO 3 ·H 2 The XRD characterization of O (commonly known as yellow tungstic acid) shows that the (111) crystal face of the material is enhanced to generate, and the experimental result shows that the material has the remarkably promoted piezoelectric catalytic hydrogen peroxide generation performance. Comparative experiment shows that the parent WS 2 The particle size and the stripping oxidation time of the catalyst have influence on the chemical structure and the catalytic performance of the target catalyst yellow tungstic acid.
Disclosure of Invention
The invention provides a preparation method of a fulvic acid catalyst and application of the fulvic acid catalyst in generation of hydrogen peroxide through piezoelectric catalysis.
A preparation method of a fulvic acid catalyst comprises the following steps:
taking tungsten disulfide (WS) 2 ) Putting the precursor in concentrated nitric acid, performing oxidation stripping by ultrasonic and stirring, and removing the precursor WS 2 WO transformed into (111) plane to enhance growth 3 ·H 2 O (yellow tungstic acid), and carrying out aftertreatment to obtain the yellow tungstic acid catalyst. The hydrogen peroxide is produced by carrying out piezoelectric catalysis in an ultrasonic mode.
The particle size of the tungsten disulfide is 80 nm-2 mu m.
The dosage ratio of the tungsten disulfide to the concentrated nitric acid is 150-250 mg:15 to 25mL, more preferably 200mg:20mL.
The mass fraction of the concentrated nitric acid is 60-70%, and the preferable mass fraction is 68%.
The ultrasonic time is 20-50 minutes.
The stirring time is 3-10 hours.
The post-treatment comprises centrifugation, washing and drying, and the washing is carried out for a plurality of times by using deionized water and ethanol until the pH of the washing solution at the last time is close to neutrality.
The method comprises the following steps of carrying out piezoelectric catalysis on the prepared yellow tungstic acid catalyst in an ultrasonic mode to generate hydrogen peroxide, and specifically comprises the following steps:
1) Dispersing a fulvic acid catalyst in a mixed solution of deionized water and isopropanol;
2) The reaction induces the hydrogen peroxide production through ultrasonic vibration provided by an ultrasonic cleaning machine, points are taken at set time intervals, and the concentration test of the hydrogen peroxide is carried out. Note: the piezoelectric catalytic reaction does not need to be exposed to any oxygen-containing gas.
In the step 1), the ratio of the dosages of the fulvic acid catalyst, the deionized water and the isopropanol is 15-25 mg: 14-24 mL:0.5 to 2mL, more preferably 20mg:19mL of: 1mL.
In the step 2), the parameters of the ultrasonic machine are 110W and 37kHz. In order to prevent excessive temperatures during sonication, ice cubes are used for cooling.
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 catalyst under the action of ultrasonic stirring by a strong oxidizing environment constructed by concentrated nitric acid, has a nano flower-like structure, and is 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 tungstic acid is convenient and easy to obtain, and can be popularized in a large scale.
(2) The target catalyst has remarkable performance of generating hydrogen peroxide by piezoelectric catalysis, the optimal performance of generating hydrogen peroxide is 23.91 (+ -1.79) millimole/hour/gram, and the target catalyst is obtained under the condition of not exposing any oxygen-containing gas. Parent WS 2 The size and the oxidation stripping time of the catalyst have influence on the chemical structure and the catalytic performance of the target catalyst, namely the yellow tungstic acid. WS (WS) 2 The smaller the grain size is, the better the performance of the prepared yellow tungstic acid in producing hydrogen peroxide by piezoelectric catalysis is. The oxidation stripping time is controlled to be 5 hours, and the performance of the prepared tungstic acid catalyst for generating hydrogen peroxide is optimal.
Drawings
FIG. 1 is a scanning electron micrograph of a catalyst WSO-T prepared in example 1;
FIG. 2 shows WSO-T, WO synthesized in example 1 and example 4 3 ·H 2 O and commercial WS 2 XRD pattern of (a);
FIG. 3 is a graph showing the adsorption and desorption curves of nitrogen and the specific surface area 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 commercial WS 2 Ultrasonic stimulation of piezoelectric catalysis to produce dioxygenA water performance map;
FIG. 5 shows WS having different particle sizes in examples 1,2 and 3 2 The prepared WSO-5 piezoelectric catalysis hydrogen peroxide production performance graph.
Detailed Description
The invention is further described in detail by the following examples in conjunction with the accompanying drawings.
1. The specific steps of the catalyst WSO-T synthesis comprise the following steps:
1) Taking a certain quality of commercial WS 2 As a precursor, add to a 100mL Erlenmeyer flask. Quality of commercial WS 2 The optimal amount after optimization is 200mg, WS 2 The optimal value after the particle size is optimized is 100nm;
2) Slowly adding a certain volume of concentrated nitric acid solution into the conical flask, wherein the optimal value of the volume of the concentrated nitric acid solution after optimization is 20mL;
3) Placing the mixture in an ultrasonic machine for ultrasonic treatment for a period of time, wherein the ultrasonic power is 37kHz, and the optimal value after the ultrasonic treatment time is optimized 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 25mL;
5) Stirring for a certain time on a stirrer, wherein the optimal value after the stirring time is optimized is 5 hours;
6) The product obtained in 5) was centrifuged and washed several times with deionized water and ethanol until the final eluate pH was close to neutral. The obtained product is abbreviated as WSO-T, and T represents the oxidation stripping time.
Example 1
1) Taking 200mg of commercial WS with the particle size of 100nm 2 Adding the precursor into a 100mL conical flask;
2) Slowly adding 20mL of concentrated nitric acid (mass fraction is 68%) into an erlenmeyer flask;
3) Placing the mixture in an ultrasonic machine for 30 minutes (the power of the ultrasonic is 37 kHz) to ensure that the WS is 2 Carrying out primary stripping;
4) After the ultrasonic treatment is finished, 25mL of deionized water is added, and the mixture is stirred on a stirrer for a certain time T, wherein T =1,2,3,5 and 10 hours;
5) The product obtained in 4) was centrifuged and washed several times with deionized water and ethanol until the final wash pH was close to neutral. The obtained product is abbreviated as WSO-T, and T represents oxidation stripping time;
6) And (3) drying the solid powder catalyst in the step 5) in an oven for later use, wherein the temperature of the oven is 60 ℃, and the time is 4 hours.
Example 2 (comparative example)
1) 200mg of commercial WS having a particle size of 27 μm 2 Adding the precursor into a 100mL conical flask;
2) Slowly adding 20mL of concentrated nitric acid (mass fraction of 68%) into the conical flask;
3) The mixture is placed in an ultrasonic machine for 30 minutes (the power of the ultrasonic is 37 kHz) so that WS is enabled to be 2 Carrying out primary stripping;
4) After the ultrasonic treatment is finished, adding 25mL of deionized water, and stirring for 5 hours on a stirrer;
5) The product obtained in 4) was centrifuged and washed several times with deionized water and ethanol until the final wash pH was close to neutral. The product obtained is abbreviated as WSO-5,5 represents oxidation stripping for 5 hours;
6) And (3) drying the solid powder catalyst in the step 5) in an oven for later use, wherein the temperature of the oven is 60 ℃, and the time is 4 hours.
Example 3
1) 200mg of commercial WS having a particle size of 2 μm 2 Adding the precursor into a 100mL conical flask;
2) Slowly adding 20mL of concentrated nitric acid (mass fraction is 68%) into an erlenmeyer flask;
3) Placing the mixture in an ultrasonic machine for 30 minutes (the power of the ultrasonic is 37 kHz) to ensure that the WS is 2 Carrying out primary stripping;
4) After the ultrasonic treatment is finished, adding 25mL of deionized water, and stirring for 5 hours on a stirrer;
5) The product obtained in 4) was centrifuged and washed several times with deionized water and ethanol until the final wash pH was close to neutral. The product obtained is abbreviated as WSO-5,5 represents oxidation stripping for 5 hours;
6) And (3) drying the solid powder catalyst in the step 5) in an oven for later use, wherein the temperature of the oven is 60 ℃, and the time is 4 hours.
Example 4 (comparative example)
1) 25mL of 0.2mol/L sodium tungstate dihydrate (Na) was taken 2 WO 4 ·2H 2 O) heating and stirring to 60 ℃ on a magnetic heating stirrer:
2) Adding 30mL of 6mol/L concentrated sulfuric acid dropwise under stirring;
3) Standing for 2 hours, WO 3 ·H 2 Gradually separating out O nano solid powder, and centrifugally washing for several times for later use.
4) And (4) drying the solid powder catalyst in the step (3) in an oven for standby, wherein the temperature of the oven is 60 ℃, and the time is 4 hours.
The application of preparing hydrogen peroxide by piezoelectric catalysis specifically comprises the following steps:
the catalyst prepared in the above embodiment is selected to perform a piezoelectric catalytic hydrogen peroxide generation process of ultrasonic stimulation. The experimental procedure was as follows:
20mg of the powdered catalyst was dispersed in a mixture of 19mL of deionized water and 1mL of isopropyl alcohol, and the initial pH of the solution was 4. The reaction is induced by ultrasonic vibration provided by an ultrasonic cleaning machine with parameters of 110W and 37kHz. In order to prevent excessive temperatures during sonication, ice cubes are used for cooling. And (4) taking points at set time intervals, and testing the concentration of hydrogen peroxide. Note: the piezoelectric catalytic reaction does not need to be exposed to any oxygen-containing gas.
2. Method of the invention
1) Taking 20mg of the catalyst prepared in the process to be placed in a mixed solution of 19mL of deionized water and 1mL of isopropanol;
2) And (3) turning on the ultrasonic machine, triggering the 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. In order to prevent the temperature from being too high during the ultrasound process, ice blocks are used for cooling.
3. Effects obtained by this example
FIG. 1 is a scanning electron micrograph of the catalyst WSO-T prepared in example 1. From FIG. 1 a) it was found that WS is commercialized 2 Exhibiting a bulk hexagonal structure, the process of ultrasonic exfoliation resulting in a bulk WS 2 The separation collapses gradually. Shows the growth of nanometer flower shape in the strong oxidizing environment. As the oxidation time increases, the lumps become smaller and the petals of the surface nanoflower become more sharp. Corresponding in sequence to FIGS. 1 b-e) are scanning electron micrographs of the samples prepared in example 1 by oxidation at 1,3,5 and 10 hour time ratios. As can be seen from the built-in graph, the edge thickness becomes thinner as the oxidation time increases.
FIG. 2 shows WSO-T, WO synthesized in example 1 and example 4 3 ·H 2 O and commercial WS 2 XRD pattern of (a). FIG. 2 a) it can be seen that WS is commercialized 2 A strong diffraction peak was exhibited at the (002) plane position. Indicating that the crystallinity is good. WO in example 4 where the catalyst is typically prepared 3 ·H 2 O, its JCPDF card number is 84-0886. However, WSO-5 prepared according to example 1 showed the same XRD pattern as the catalyst prepared in example 4, indicating that WSO-5 is a yellow tungstic acid. Except that the (111) crystal plane in WSO-5 gave enhanced growth. Figure 2 b) is the XRD pattern of the WSO-T samples at different oxidation times. Interestingly, at relatively short oxidative strip times, such as WSO-1 and WSO-2, the parent WS 2 The (002) plane of (1) is still retained. With oxidation stripping times over 3 hours, WS 2 The peak at (002) plane in (1) was completely disappeared to obtain pure WO 3 ·H 2 And O. For the sake of accurate expression, we expressed the sample prepared in example 1 as WSO-T.
FIG. 3 is a graph showing the adsorption and desorption curves of nitrogen and the specific surface area 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 higher relative pressures (> 0.5), a hysteresis loop appears, indicating the presence of a macroporous structure in the catalyst. This indicates that the strongly oxidizing environment promotes vacancies in the bulk material. Their specific surface areas were obtained according to the BET calculation method, as shown in FIG. 3b. Stripping with oxidationThe separation proceeded, the specific surface area of the catalyst gradually increased, from 3.33m of the precursor 2 The increase in/g reaches a maximum of 39.4m 2 (ii) a more than 10-fold increase per g (WSO-10).
FIG. 4 is a graph comparing the catalytic production of hydrogen peroxide in different systems. Commercial WS as in FIG. 4a 2 The product shows almost no generation capability of hydrogen peroxide, while WSO-5 has remarkable hydrogen peroxide generation performance, and the yield reaches 478.12 (+ -25.33) mu m in 1 hour of reaction. It is worth mentioning that the excellent hydrogen peroxide production performance is obtained by only using the natural solution oxygen in the system under the condition of not exposing any oxygen-containing gas. When the external vibration condition is removed, the WSO-5 catalyst shows the performance of hardly generating hydrogen peroxide. This indicates that the excellent hydrogen peroxide generation capability of WSO-5 comes from the piezoelectric catalysis process. For comparison, WO synthesized by liquid phase deposition in example 4 3 ·H 2 O also shows negligible yield with piezo-catalyzed hydrogen peroxide preparation. The results show that WSO-5 produced by (111) crystal face enhancement in example 1 has excellent hydrogen peroxide piezoelectric catalytic generation capability, and is not possessed by common yellow tungstic acid. FIG. 4b is a UV-visible absorption curve of hydrogen peroxide generated by POD/DPD method detection of WSO-5.
We explored the hydrogen peroxide production performance of WSO-T series catalysts, see FIG. 4c. With the increase of the oxidation time, WSO-T shows enhanced hydrogen peroxide generation performance. The catalyst WSO-1 has the weakest hydrogen peroxide production performance, the WSO-5 reaches the optimal value, and the WSO-10 is reduced. Therefore, the WSO-5 catalyst is the best performing catalyst, and the oxidation stripping time for the catalysts prepared in examples 2 and 3 is 5 hours. FIG. 4d shows the highest yield of WSO-5 at 23.91 (+ -1.79) m μm/h/g for WSO-T in relation to hydrogen peroxide.
FIG. 5 shows WS having different particle sizes in examples 1,2 and 3 2 (figure 5 a) the performance diagram of the piezoelectric catalysis hydrogen peroxide generation of the WSO-5 prepared. According to the experimental results, WS of different particle sizes 2 WSO-5 prepared from the matrix has influence on the performance of piezoelectric catalysis for generating hydrogen peroxide. 100nm sized parent WS 2 The WSO-5 prepared has the best performance of generating hydrogen peroxide, and the WS of 27 mu m 2 The performance of the prepared WSO-5 piezoelectric catalysis hydrogen peroxide is the worst. WS of smaller particle size 2 The WSO-5 prepared by the matrix has thinner edge nano petals. It is more favorable for the full contact of three-phase interfaces and the catalytic reaction in the electron transmission.

Claims (10)

1. The preparation method of the fulvic acid catalyst is characterized by comprising the following steps of:
putting tungsten disulfide serving as a matrix into concentrated nitric acid, carrying out oxidation stripping by ultrasonic and stirring, and carrying out aftertreatment to obtain the fulvic acid catalyst.
2. The method of claim 1, wherein the tungsten disulfide has a particle size of 80nm to 2 μm.
3. The method for preparing the fulvic acid catalyst of claim 1, wherein the ratio of the amount of tungsten disulfide to concentrated nitric acid is 150-250 mg: 15-25 mL.
4. The method for preparing the fulvic acid catalyst according to claim 1, wherein the mass fraction of the concentrated nitric acid is 60% to 70%.
5. The method for preparing a fulvic acid catalyst according to claim 1, wherein the sonication time is between 20 and 50 minutes.
6. The method of claim 1, wherein the stirring time is 3 to 10 hours.
7. The method of claim 1, wherein the post-treatment comprises centrifugation, washing and drying, and the washing is performed several times with deionized water and ethanol until the pH of the last washing solution is near neutral.
8. Use of the xanthotungic acid catalyst prepared according to the process of any one of claims 1 to 7 in the production of hydrogen peroxide by piezoelectric catalysis.
9. The use according to claim 8, comprising:
1) Dispersing a fulvic acid catalyst in a mixed solution of deionized water and isopropanol;
2) The reaction induces the hydrogen peroxide production through the ultrasonic vibration provided by the ultrasonic cleaning machine.
10. The use according to claim 9, wherein in step 1), the ratio of the amounts of the fulvic acid catalyst, the deionized water and the isopropyl alcohol is 15-25 mg: 14-24 mL: 0.5-2 mL.
CN202211055634.8A 2022-08-31 2022-08-31 Preparation method of yellow-tungstic acid catalyst and application of yellow-tungstic acid catalyst in piezocatalysis of hydrogen peroxide Active CN115448367B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
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

Patent Citations (5)

* Cited by examiner, † Cited by third party
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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