CN113333010B - Photocatalyst nitrogen-doped SrMoO4Preparation method of (1) - Google Patents

Photocatalyst nitrogen-doped SrMoO4Preparation method of (1) Download PDF

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CN113333010B
CN113333010B CN202110599066.7A CN202110599066A CN113333010B CN 113333010 B CN113333010 B CN 113333010B CN 202110599066 A CN202110599066 A CN 202110599066A CN 113333010 B CN113333010 B CN 113333010B
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srmoo
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CN113333010A (en
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戴振翔
朱力为
郑赣鸿
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Anhui University
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    • B01J35/39
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24Chromium, molybdenum or tungsten
    • B01J23/28Molybdenum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24Nitrogen compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/30Treatment of water, waste water, or sewage by irradiation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/308Dyes; Colorants; Fluorescent agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/10Photocatalysts

Abstract

Photocatalyst nitrogen-doped SrMoO4Relates to the technical field of photocatalyst material preparation. First using ammonium heptamolybdate tetrahydrate (NH)4)6Mo7O24·4H2O and strontium nitrate Sr (NO)3)2Preparation of SrMoO by hydrothermal method4Then through urea CH4N2O is doped with nitrogen element, and nitrogen-doped SrMoO is prepared by adopting a steam thermal method4A photocatalyst. According to the invention, the nitrogen-doped strontium molybdate is prepared by adopting a hydrothermal method and a steam thermal method, and the preparation method has the advantages of safe and easily-obtained raw materials, simple process steps, no pollution and low equipment requirement. The prepared nitrogen-doped strontium molybdate photocatalyst can effectively degrade methylene blue solution, has high photocatalytic activity, and can be repeatedly used.

Description

Photocatalyst nitrogen-doped SrMoO4Preparation method of (1)
Technical Field
The invention relates to the technical field of photocatalyst material preparation, in particular to a photocatalyst nitrogen-doped SrMoO4The preparation method of (1).
Background
Photocatalytic degradation of organic pollutants means that the organic pollutants undergo oxidative decomposition reaction under the irradiation of light (visible light or ultraviolet light) and are finally degraded into small molecular substances such as carbon dioxide, water and inorganic ions, and the photocatalytic degradation method is the most promising pollution treatment method at present.
SrMoO4Is a molybdate with a tetragonal crystal system, MoO, belonging to a scheelite structure4 2-The ion is composed of four completely equivalent O ions centered around the Mo ion and exhibits a tetrahedrally symmetric morphology. Sr ions having a valence of +2 are likewise surrounded by eight O atoms, so that Sr ions and MoO4 2-The ions share 8O ions adjacent at the top corner. The tetrahedral structure has very strong stability and is a main lattice junctionThe structure is not easily changed. Because of its good stability, no pollution and easy synthesis, it has many applications in different fields.
PbMoO in the presence of molybdate with scheelite structure4In the experiments and researches, PbMoO is found4TiO with a classical photocatalyst2The close forbidden band width is about 3.3eV, and the photocatalytic performance is also excellent. Therefore, SrMoO can be reduced sufficiently when the forbidden band width can be reduced sufficiently4Perhaps with the potential to be a good photocatalyst.
Synthetic preparation of SrMoO is known4The methods of the nano material are various, and mainly include a coprecipitation method, a microwave radiation method, an electrochemical method, a hydrothermal method, a sol-gel method and the like. However, SrMoO prepared using a different method4The sample morphology will also be different and its photocatalytic performance will also be significantly different.
Disclosure of Invention
Aiming at overcoming the SrMoO prepared in the prior art4The invention aims to provide a photocatalyst nitrogen-doped SrMoO with a too large forbidden bandwidth4The preparation method of (1). The photocatalyst SrMoO is prepared4Has the characteristics of higher photocatalytic activity and the like, and can be repeatedly used for many times.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
photocatalyst nitrogen-doped SrMoO4The preparation method of (1) first utilizes ammonium heptamolybdate tetrahydrate (NH)4)6Mo7O24·4H2O and strontium nitrate Sr (NO)3)2Preparation of SrMoO by hydrothermal method4Then through urea CH4N2O is doped with nitrogen element, and nitrogen-doped SrMoO is prepared by adopting a steam thermal method4A photocatalyst.
Further, the photocatalyst is nitrogen-doped SrMoO4The preparation method comprises the following steps:
1) sr (NO) nitrate according to the stoichiometric ratio3)2With ammonium heptamolybdate tetrahydrate (NH)4)6Mo7O24·4H2Dissolving O in deionized water respectively, and placing the mixture on a magnetic stirrer for stirring;
2) stirring while slowly adding strontium nitrate Sr (NO)3)2Ammonium heptamolybdate tetrahydrate (NH) is added dropwise to the aqueous solution4)6Mo7O24·4H2Mixing the O aqueous solution, and then dripping NaOH solution to adjust the pH value of the mixed solution;
3) pouring the mixed solution into a high-temperature high-pressure reaction kettle to carry out hydrothermal reaction; after the reaction is finished, waiting for the reaction kettle to be naturally cooled to room temperature, taking out the obtained sample, centrifuging by using a centrifuge, washing by using deionized water and absolute ethyl alcohol, and finally drying the sample;
4) drying SrMoO4Dissolving a sample in deionized water, and placing the sample in an ultrasonic cleaner for ultrasonic dissolution to obtain SrMoO4An aqueous solution;
5) adding urea CH4N2O to SrMoO4In the water solution, ultrasonic mixing;
6) pouring the mixed liquid after ultrasonic treatment into a high-temperature high-pressure reaction kettle, and carrying out steam thermal reaction to obtain the final N-doped SrMoO4A photocatalyst.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
and 2) dripping NaOH solution into the mixture to adjust the pH value of the mixed solution to be 6-9, adjusting the hydrothermal reaction temperature in the step 3) to be 120 ℃, reacting for 360 min, adding urea into the mixture in the step 5) according to the molar ratio of N to Sr of 0.05-0.6, ultrasonically mixing the mixture for 20min after adding the urea, and adjusting the steam thermal reaction temperature in the step 6) to be 180 ℃ and the reaction time to be 720 min.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the nitrogen-doped strontium molybdate is prepared by adopting a hydrothermal method and a steam thermal method, and the preparation method has the advantages of safe and easily-obtained raw materials, simple process steps, no pollution and low equipment requirement. The prepared nitrogen-doped strontium molybdate photocatalyst can effectively degrade methylene blue solution, has high photocatalytic activity, and can be repeatedly used.
Drawings
FIG. 1 shows SrMoO4Nitrogen-doped strontium molybdate SrMoO obtained in examples 4 to 64X-ray diffraction pattern of photocatalyst (corresponding to doping ratio of 0.2, 0.4, 0.6); wherein the abscissa is the diffraction angle 2 θ, and the ordinate is the relative intensity I.
FIG. 2 shows SrMoO4Nitrogen-doped strontium molybdate SrMoO obtained in examples 1 to 64UV-vis spectrum of photocatalyst (corresponding doping ratio of 0.05, 0.1, 0.15, 0.2, 0.4, 0.6); wherein the abscissa is wavelength and the ordinate is absorbance.
FIG. 3 is a graph of the nitrogen-doped strontium molybdate SrMoO obtained in example 4 (corresponding to a doping ratio of 0.2)4Fitting graph of forbidden band width of photocatalyst. Wherein the abscissa is the energy h v and the ordinate is (alpha h v)2
FIG. 4 shows SrMoO4Nitrogen-doped strontium molybdate SrMoO obtained in examples 1 to 64Photocatalytic performance data curves for photocatalysts (corresponding to doping ratios of 0.05, 0.1, 0.15, 0.2, 0.4, 0.6); wherein, the abscissa is the illumination time, and the ordinate is the degradation rate.
Detailed Description
The present invention will be described in further detail with reference to the following examples and accompanying drawings.
Example 1
Photocatalyst nitrogen-doped SrMoO4(the nitrogen doping ratio is 0.05), the preparation method comprises the following steps:
1) 2.5775g of strontium nitrate Sr (NO) in a stoichiometric ratio3)2With 2.1611g of ammonium heptamolybdate tetrahydrate (NH)4)6Mo7O24·4H2O is dissolved in 100 mL of deionized water and placed on a magnetic stirrer to be stirred.
2) Under the condition of stirring, slowly adding strontium nitrate Sr (NO)3)2Ammonium heptamolybdate tetrahydrate (NH) is added dropwise to the aqueous solution4)6Mo7O24·4H2Mixing the O aqueous solution, and then dripping NaOH solution (96 percent by mass) to adjust the pH value of the mixed solution to about 7.
3) And pouring the mixed solution into a high-temperature high-pressure reaction kettle (Parr 4577) to carry out hydrothermal reaction at the reaction temperature of 120 ℃ for 360 min. And after the reaction is finished, waiting for the reaction kettle to be naturally cooled to room temperature, taking out the obtained sample, centrifuging (4000 r/min) by using a centrifuge, washing for 6-7 times by using deionized water and absolute ethyl alcohol, and finally drying the sample at 80 ℃.
4) 300 mg of SrMoO4Pouring the sample into a beaker, adding the sample into 100 mL of deionized water, placing the beaker into an ultrasonic cleaning machine, and ultrasonically dissolving for 10 min to obtain SrMoO4An aqueous solution.
5) Calculating the required urea quantity according to the molar ratio of N to Sr of 0.05, and adding urea CH4N2O to SrMoO4In the water solution, ultrasonic mixing is carried out for 20 min.
6) Pouring the mixed solution after ultrasonic treatment into a quartz cup, putting the quartz cup into a 1000 mL Hastelloy high-temperature high-pressure reaction kettle (parr 4500, US), and filling 150 mL deionized water into an outer reaction kettle. And starting the reaction kettle after the preparation work of the reaction kettle is finished, setting the reaction temperature to be 180 ℃, and setting the reaction time to be 720 min.
7) And taking out the quartz cup after the reaction kettle is naturally cooled to room temperature, washing for 3-4 times, and drying to obtain a final N-doped sample (the corresponding doping ratio is 0.05).
Examples 2 to 6
The difference from the embodiment 1 is only that the molar ratio of N to Sr is 0.1, 0.15, 0.2, 0.4 and 0.6 in sequence, and other process parameters are completely the same.
Example 1-6 Performance characterization
1. X-ray diffraction test
Separately testing SrMoO by X-ray powder diffractometer (XRD)4Example 1, step 3, the same applies below) Nitrogen-doped strontium molybdate SrMoO prepared in examples 4-64The photocatalytic material, as can be seen from the position and relative intensity of each diffraction peak in fig. 1 compared with the standard PDF card (JCPDS 08-0482), the prepared sample is the strontium molybdate photocatalytic material. The nitrogen doping has promotion effect on the improvement of the photocatalytic performance of strontium molybdate, and each spectral peak in a spectrogram is sharp, so that sample crystals are shownThe degree of conversion was good.
2. Ultraviolet-visible light test
Separately testing SrMoO with an ultraviolet spectrophotometer (UV; UV-3600)4Nitrogen-doped strontium molybdate SrMoO prepared in examples 1-64The UV-vis spectrum of the photocatalytic material, for each sample, is shown in FIG. 2. The forbidden band width of the sample is obtained after Gaussian fitting, the forbidden band width of the doped strontium molybdate photocatalytic material is 3.74-4.14 eV, and the forbidden band width of the N0.2 sample (prepared in example 4) is 3.75 eV (as shown in FIG. 3).
3. Photocatalytic experimental testing
Separately testing SrMoO with an ultraviolet spectrophotometer (UV; UV-3200S)4Strontium SrMoO molybdate prepared in examples 1 to 64The catalytic performance of the photocatalytic material is shown in fig. 4, the prepared nitrogen-doped strontium molybdate photocatalytic material takes methylene blue as a simulated pollutant, and the strontium molybdate photocatalytic degradation rate with the doping ratio of 0.2 reaches 83% after 100 minutes, which shows that the nitrogen doping can improve the photocatalytic activity of strontium molybdate.
In conclusion, it can be seen from the analysis results of the XRD chart, the UV chart and the photocatalytic degradation rate chart that the nitrogen-doped strontium molybdate photocatalyst prepared by the hydrothermal synthesis method can effectively degrade methylene blue solution and has higher photocatalytic activity.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.

Claims (5)

1. Photocatalyst nitrogen-doped SrMoO4Is characterized in that ammonium heptamolybdate tetrahydrate (NH) is firstly utilized4)6Mo7O24·4H2O and strontium nitrate Sr (NO)3)2Preparation of SrMoO by hydrothermal method4Then through urea CH4N2Doping nitrogen element with O, and adopting steam heating methodPreparing to obtain nitrogen-doped SrMoO4The photocatalyst comprises the following steps:
1) sr (NO) nitrate according to the stoichiometric ratio3)2With ammonium heptamolybdate tetrahydrate (NH)4)6Mo7O24·4H2Dissolving O in deionized water respectively, and placing the mixture on a magnetic stirrer for stirring;
2) stirring while slowly adding strontium nitrate Sr (NO)3)2Ammonium heptamolybdate tetrahydrate (NH) is added dropwise to the aqueous solution4)6Mo7O24·4H2Mixing the O aqueous solution, and then dripping NaOH solution to adjust the pH value of the mixed solution;
3) pouring the mixed solution into a high-temperature high-pressure reaction kettle to carry out hydrothermal reaction; after the reaction is finished, waiting for the reaction kettle to be naturally cooled to room temperature, taking out the obtained sample, centrifuging by using a centrifuge, washing by using deionized water and absolute ethyl alcohol, and finally drying the sample;
4) drying SrMoO4Dissolving a sample in deionized water, and placing the sample in an ultrasonic cleaner for ultrasonic dissolution to obtain SrMoO4An aqueous solution;
5) adding urea CH4N2O to SrMoO4In the water solution, ultrasonic mixing;
6) pouring the mixed solution after ultrasonic treatment into a quartz cup, putting the quartz cup into a 1000 mL Hastelloy high-temperature high-pressure reaction kettle, and putting 150 mL deionized water into an outer reaction kettle; starting the reaction kettle after the preparation work is finished, setting the reaction temperature to be 180 ℃, and the reaction time to be 720 min, and reacting to obtain the final N-doped SrMoO4A photocatalyst.
2. The photocatalyst nitrogen-doped SrMoO of claim 14The preparation method is characterized in that NaOH solution is dropped into the solution obtained in the step 2) to adjust the pH value of the mixed solution to 6-9.
3. The photocatalyst nitrogen-doped SrMoO of claim 14The preparation method is characterized in that the hydrothermal reaction temperature in the step 3) is 120 ℃, and the reaction time is360 min。
4. The photocatalyst nitrogen-doped SrMoO of claim 14The preparation method is characterized in that urea is added in the step 5) according to the molar ratio of N to Sr of 0.05-0.6.
5. The photocatalyst nitrogen-doped SrMoO of claim 14The preparation method is characterized in that the urea is added in the step 5) and then ultrasonic mixing is carried out for 20 min.
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CN106390974A (en) * 2016-09-13 2017-02-15 安徽大学 Preparation method of efficient photocatalyst SrTiO3
WO2018232133A1 (en) * 2017-06-15 2018-12-20 North Carolina State University Oxygen carrying materials with surface modification for redox-based catalysis and methods of making and uses thereof
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Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101036878A (en) * 2007-04-06 2007-09-19 武汉理工大学 Steam heat method for preparing high-crystallized nanocrystalline titanium dioxide photocatalyst
CN105984902A (en) * 2016-02-19 2016-10-05 安徽大学 Preparation method of strontium-molybdate-dopable nano material
CN106390974A (en) * 2016-09-13 2017-02-15 安徽大学 Preparation method of efficient photocatalyst SrTiO3
WO2018232133A1 (en) * 2017-06-15 2018-12-20 North Carolina State University Oxygen carrying materials with surface modification for redox-based catalysis and methods of making and uses thereof
CN110898827A (en) * 2019-12-11 2020-03-24 哈尔滨芳新佳环保科技有限公司 Method for preparing tungsten photocatalyst heterojunction through doping induction
CN112221529A (en) * 2020-11-12 2021-01-15 郭绍香 Bi-B doped SrWO4/Ba-g-C3N4Composite nitrogen-fixing photocatalyst and preparation method thereof

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Title
Li~+离子共掺SrWO_4:5%Tb~(3+)绒球的制备及其荧光性能;陶萍芳等;《玉林师范学院学报》;20191001(第05期);第90-95页 *

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