CN113860388A - Sodium citrate-assisted synthesis cobalt tungstate material and preparation method and application thereof - Google Patents

Sodium citrate-assisted synthesis cobalt tungstate material and preparation method and application thereof Download PDF

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CN113860388A
CN113860388A CN202111077583.4A CN202111077583A CN113860388A CN 113860388 A CN113860388 A CN 113860388A CN 202111077583 A CN202111077583 A CN 202111077583A CN 113860388 A CN113860388 A CN 113860388A
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sodium citrate
cobalt tungstate
tungstate material
assisted synthesis
carrying
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CN113860388B (en
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王思幻
徐亮
刘妮萍
张琳
吴学签
王新
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Liaoning University
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Liaoning University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

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Abstract

The invention belongs to the technical field of water pollution protection, and particularly relates to a cobalt tungstate material synthesized by sodium citrate in an auxiliary manner, and a preparation method and application thereof. Mixing Co (NO)3)2·6H2O and Na2WO4·2H2Dissolving O in deionized water respectively; mixing the two solutions, adding sodium citrate, and magnetically stirring at room temperature; then carrying out ultrasonic reaction, pouring into a reaction kettle, and carrying out high-temperature reaction; cooling to room temperature, carrying out suction filtration to collect a product, and drying to obtain the product. The performance of the cobalt tungstate material for degrading pollutants by acoustic catalysis is obviously improved.

Description

Sodium citrate-assisted synthesis cobalt tungstate material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of water pollution protection, and particularly relates to a cobalt tungstate material synthesized by sodium citrate in an auxiliary manner, and a preparation method and application thereof.
Background
The morphology of the material is closely related to the synthesis method thereof. The hydrothermal method is widely applied to the synthesis of cobalt tungstate nano materials. To date, hydrothermally synthesized cobalt tungstate has different micro/nano structures including nanorods, microspheres and echinoid morphologies. Sodium citrate is an important auxiliary agent in the hydrothermal process, and the carboxylic acid group and the hydroxyl group of the sodium citrate can strongly chelate metal ions. Therefore, during hydrothermal processes, the decrease of free metal ions slows down the nucleation rate and crystal growth of the precursor, thereby affecting the morphology of the final product.
The morphology, area exposure and size of the acoustic catalyst have a significant impact on acoustic catalytic performance. Nanostructured acoustic catalysts can exhibit cellular catalytic activity because acoustic catalyst morphology and particle size have a significant impact on optical and electronic performance, which in turn affects acoustic catalytic activity.
Disclosure of Invention
The invention aims to provide a method for improving the acoustic catalytic activity of a cobalt tungstate composite material synthesized by sodium citrate in an auxiliary manner.
The technical scheme adopted by the invention is as follows: a sodium citrate-assisted synthesis of cobalt tungstate material is prepared by mixing Co (NO)3)2·6H2O and Na2WO4·2H2Dissolving O in deionized water respectively; mixing the two solutions, adding sodium citrate, and magnetically stirring at room temperature; then carrying out ultrasonic reaction, pouring into a reaction kettle, and carrying out high-temperature reaction; cooling to room temperature, carrying out suction filtration to collect a product, and drying to obtain the product.
The sodium citrate-assisted synthesis of the cobalt tungstate material adopts Co (NO) according to the molar ratio3)2·6H2O：Na2WO4·2H2O: the citric acid is 1:1: 0.1-1.
The ultrasonic reaction time of the sodium citrate-assisted synthesis of the cobalt tungstate material is 0.5 h.
The synthesis temperature of the sodium citrate-assisted synthesis cobalt tungstate material is 180 ℃, and the synthesis time is 24 hours.
The sodium citrate-assisted synthesis of the cobalt tungstate material is applied to degradation of organic pollutants.
The application and the method are as follows: adding a cobalt tungstate material synthesized by sodium citrate with the assistance of the organic pollutant solution, and performing ultrasonic catalysis.
In the application, the addition amount of the cobalt tungstate acoustic catalyst synthesized by sodium citrate assistance is 1 g/L.
In the application, the concentration of the organic pollutants is 4.5 mg/L.
The use as described above, wherein the organic contaminant is methylene blue.
The invention has the beneficial effects that: the size and thickness of the nano-plate can be simply adjusted by changing the addition amount of sodium citrate. The morphology-controllable cobalt tungstate material can be obtained by sodium citrate-assisted hydrothermal synthesis, so that the acoustic catalytic activity of the cobalt tungstate material is improved.
Drawings
FIG. 1 is a CoWO prepared in example 14CoWO prepared in-0 and example 24-4 XRD diffraction pattern of the composite acoustic catalyst, wherein a is CoWO4-4, b is CoWO4-0。
FIG. 2 is a CoWO prepared in example 14CoWO prepared in-0 and example 24-4 XPS spectra of composite acoustic catalysts, wherein a is CoWO4-4, b is CoWO4-0。
FIG. 3 is pure CoWO prepared in example 14And the degradation efficiency of the acoustic catalyst prepared in example 2 for degrading methylene blue.
Detailed Description
Example 1CoWO4Preparation of
First Co (NO)3)2·6H2O (5mmol) was dissolved in 30mL deionized water to give an aqueous solution labeled A, Na was added2WO4·2H2O (5mmol) is dissolved in 30mL deionized water and is marked as solution B; mixing A and B, and magnetically stirring at room temperature for 0.5 h; the reaction was further carried out by ultrasonic reaction for 0.5h and the homogeneous suspension was then sealed in a 100ml autoclave lined with polytetrafluoroethylene, kept at 180 ℃ for 24h and then cooled naturally to room temperature. Suction filtering, washing for several times, centrifugal separation to collect precipitate, and vacuum drying at 60 deg.c for 2 hr. The product CoWO is obtained4Is denoted as CoWO4-0。
Example 2 preparation of sodium citrate-assisted synthetic cobalt tungstate
First Co (NO)3)2·6H2O (5mmol) was dissolved in 30mL deionized water to give an aqueous solution labeled A, Na was added2WO4·2H2O (5mmol) is dissolved in 30mL deionized water and is marked as solution B; mixing A and B, adding sodium citrate (0.1474g, 0.3676g, 0.7353g, 1.475g) with different masses, and magnetically stirring at room temperature for 0.5 h; the reaction was further carried out by ultrasonic reaction for 0.5h and the homogeneous suspension was then sealed in a 100ml autoclave lined with polytetrafluoroethylene, kept at 180 ℃ for 24h and then cooled naturally to room temperature. Pumping filtration and washing for many times, centrifugally separating and collecting precipitate, and finally drying for 2 hours in vacuum at 60 ℃ to obtain a product CoWO4Respectively denoted as CoWO4-1，CoWO4-2，CoWO4-3，CoWO4-4。
Example 3 characterization analysis of sodium citrate-assisted synthesized cobalt tungstate acoustic catalyst
FIG. 1 is a diagram of synthetic CoWO4And sodium citrate-assisted synthetic CoWO4-2 XRD spectrum of sample. The diffraction peaks in the figure are strong and sharp, indicating that the synthesized product has higher crystallinity.
FIG. 2 is a diagram of synthetic CoWO4And sodium citrate-assisted synthetic CoWO4-2 XPS spectra of samples. The high resolution spectral signals of W4f, Co 2p, and O1s appear at 50.3eV, 812.3eV, and 545.3eV, respectively, demonstrating compounds with valences of W, Co and O of +6, +2, and-2, respectively. The high-resolution spectral signals of all elements in the cobalt tungstate nanometer material synthesized by adding sodium citrate are very close to the description of the literature, which indicates that the product synthesized by adding sodium citrate is still CoWO4And (3) nano materials.
Example 4 CoWO Synthesis with sodium citrate assistance4Influence on the effect of catalyzing ultrasonic degradation of methylene blue solution
The acoustic catalytic performance of the catalyst on methylene blue degradation was studied. In a typical degradation process, 20mL of methylene blue solution (4.5mg/L) was added to a 250mL Erlenmeyer flask, and 20mg of CoWO was added separately4-0，CoWO4-1，CoWO4-2，CoWO4-3，CoWO4-4 of a catalyst. After 120min of sonication, the catalyst particles were separated from the dye solution by centrifugation and the absorbance of the remaining methylene blue was measured by uv-vis spectrophotometer.
The formula is that the percent (%) degradation is [ (A)0-At)/A0]×100％
A0Is the initial absorbance of the methylene blue solution;
Atis the absorbance of methylene blue solution under different experimental conditions;
as can be seen from the figure, CoWO increases the amount of sodium citrate added4The degradation rate of methylene blue is increased and then decreased. The results show that CoWO synthesized by different sodium citrates4Different in morphology and different in acoustic catalytic effect. Wherein, CoWO synthesized when the proportion of sodium citrate is 25 percent is added4The highest rate of acoustic catalytic degradation. This may be due to CoWO at this time4The agglomeration among single crystals is more obvious, the specific surface area is larger, and the reaction is greatly contributed.

Claims (9)

1. A sodium citrate-assisted synthesis cobalt tungstate material is characterized in that: mixing Co (NO)3)2·6H2O and Na2WO4·2H2Dissolving O in deionized water respectively; mixing the two solutions, adding sodium citrate, and magnetically stirring at room temperature; then carrying out ultrasonic reaction, pouring into a reaction kettle, and carrying out high-temperature reaction; cooling to room temperature, carrying out suction filtration to collect a product, and drying to obtain the product.
2. The sodium citrate-assisted synthesis cobalt tungstate material as claimed in claim 1, wherein Co (NO) is added according to molar ratio3)2·6H2O：Na2WO4·2H2O: the citric acid is 1:1: 0.1-1.
3. The sodium citrate-assisted synthesis cobalt tungstate material as claimed in claim 2, wherein the ultrasonic reaction time is 0.5 h.
4. The sodium citrate-assisted synthesis cobalt tungstate material as claimed in claim 3, wherein the synthesis temperature is 180 ℃ and the synthesis time is 24 h.
5. The use of the sodium citrate-assisted synthesis of cobalt tungstate material as claimed in any one of claims 1 to 4 in the degradation of organic pollutants.
6. Use according to claim 5, characterized in that the method is as follows: adding a cobalt tungstate material synthesized by sodium citrate with the assistance of the organic pollutant solution, and performing ultrasonic catalysis.
7. The use of claim 6, wherein the amount of the cobalt tungstate acoustic catalyst for sodium citrate-assisted synthesis is 1 g/L.
8. Use according to claim 7, wherein the concentration of the organic contaminant is 4.5 mg/L.
9. The use according to claim 8, wherein the organic contaminant is methylene blue.
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US20080236441A1 (en) * 2006-10-13 2008-10-02 Ken Nobe Aqueous eletrodeposition of magnetic cobalt-samarium alloys
CN101857260A (en) * 2010-06-29 2010-10-13 上海大学 Method for preparing spherical cerium dioxide nano material with square-sheet surface structure by hydrothermal method
CN106544019A (en) * 2016-09-19 2017-03-29 沈阳化工大学 A kind of morphology controllable NaGd (MoO4)2:Eu3+The preparation method of luminescent powder
CN111229243A (en) * 2020-02-07 2020-06-05 辽宁大学 Surfactant-assisted synthesis of cobalt tungstate nanoparticles and preparation method and application thereof
CN112264004A (en) * 2020-11-25 2021-01-26 安徽大学 Catalytic material based on tungstate and application thereof in hydrogen peroxide production through water oxidation

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Publication number Priority date Publication date Assignee Title
JP2007269834A (en) * 2006-03-30 2007-10-18 Honda Motor Co Ltd Antifreeze liquid/cooling liquid composition for magnesium or magnesium alloy
US20080236441A1 (en) * 2006-10-13 2008-10-02 Ken Nobe Aqueous eletrodeposition of magnetic cobalt-samarium alloys
CN101857260A (en) * 2010-06-29 2010-10-13 上海大学 Method for preparing spherical cerium dioxide nano material with square-sheet surface structure by hydrothermal method
CN106544019A (en) * 2016-09-19 2017-03-29 沈阳化工大学 A kind of morphology controllable NaGd (MoO4)2:Eu3+The preparation method of luminescent powder
CN111229243A (en) * 2020-02-07 2020-06-05 辽宁大学 Surfactant-assisted synthesis of cobalt tungstate nanoparticles and preparation method and application thereof
CN112264004A (en) * 2020-11-25 2021-01-26 安徽大学 Catalytic material based on tungstate and application thereof in hydrogen peroxide production through water oxidation

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