WO2021052257A1 - Black bismuth tungstate photocatalyst, preparation method, and application - Google Patents

Black bismuth tungstate photocatalyst, preparation method, and application Download PDF

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WO2021052257A1
WO2021052257A1 PCT/CN2020/114816 CN2020114816W WO2021052257A1 WO 2021052257 A1 WO2021052257 A1 WO 2021052257A1 CN 2020114816 W CN2020114816 W CN 2020114816W WO 2021052257 A1 WO2021052257 A1 WO 2021052257A1
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bismuth tungstate
treatment
black
dielectric barrier
barrier discharge
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PCT/CN2020/114816
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French (fr)
Chinese (zh)
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许晖
朱兴旺
莫曌
李启笛
杨金曼
李华明
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江苏大学
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Priority to GB2105335.0A priority Critical patent/GB2592516A/en
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    • B01J35/39—
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts 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
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts 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
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
    • B01J35/30—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/347—Ionic or cathodic spraying; Electric discharge
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/40—Carbon monoxide

Definitions

  • the invention relates to a preparation method of a black bismuth tungstate photocatalyst, belonging to the technical field of preparation methods of photocatalytic materials, and the specific application direction is photocatalytic CO 2 reduction.
  • Bismuth tungstate (Bi 2 WO 6 ), as a photocatalyst with a certain visible light response, has been widely studied and applied in the degradation of organic pollutants and CO 2 reduction.
  • the high carrier recombination rate of the traditional bismuth tungstate catalyst affects its photocatalytic efficiency. Therefore, the modification of the traditional bismuth tungstate catalyst to improve its photocatalytic efficiency becomes more and more important.
  • the existing photocatalyst modification methods mainly include morphology control, precious metal deposition, semiconductor recombination and defect control. In recent years, the use of plasma to modify the surface of the photocatalyst can greatly improve the catalytic performance.
  • Plasma refers to a gas that is partially or completely ionized, and the sum of the positive and negative charges carried by free electrons and ions completely cancels out, showing electrical neutrality on a macroscopic scale.
  • the temperature of the plasma it can be divided into high-temperature plasma (thermonuclear fusion plasma) and low-temperature plasma.
  • Low-temperature plasma includes thermal plasma (plasma arc, plasma torch, etc.) and cold plasma (low-pressure AC and DC, radio frequency, microwave plasma, high-pressure dielectric barrier discharge, corona discharge, RF discharge, etc.).
  • thermal plasma plasma arc, plasma torch, etc.
  • cold plasma low-pressure AC and DC, radio frequency, microwave plasma, high-pressure dielectric barrier discharge, corona discharge, RF discharge, etc.
  • active particles in the low-temperature cold plasma which can react with the surface of the material in contact, so they are used to modify the surface of the material.
  • Dielectric barrier discharge is a non-equilibrium gas discharge with an insulating medium inserted into the discharge space, also known as dielectric barrier corona discharge or silent discharge.
  • Dielectric barrier discharge can work at high pressure and a wide frequency range, and can usually generate plasma under normal pressure.
  • the power frequency can range from 50 Hz to 1 MHz.
  • Dielectric barrier discharge plasma processing photocatalyst has the characteristics of mild processing conditions, short reaction time, and low energy consumption.
  • the purpose of the present invention is to address the disadvantages of low visible light utilization of traditional bismuth tungstate photocatalyst materials, use dielectric barrier discharge to generate plasma in different atmospheres, and process white bismuth tungstate to obtain black bismuth tungstate photocatalyst, plasma
  • the bulk treatment reduces the bismuth element on the surface of the bismuth tungstate, promotes the separation of photogenerated holes and electrons, broadens the light absorption range, and improves the photocatalytic CO 2 reduction ability.
  • a preparation method of black bismuth tungstate photocatalyst includes the following steps:
  • step (1) the amount of white bismuth tungstate is 5-20mg; the amount of absolute ethanol is 2-4mL; the ultrasonic power is 100-150W, the ultrasonic time is 5-10min; the quartz plate used The thickness is 0.5mm.
  • the dielectric barrier discharge power is 50-100 W; the reaction gas is argon, ammonia or hydrogen, the treatment time is 1-5 min, and the gas flow rate is 100-200 mL/min.
  • step (3) the amount of the absolute ethanol is 1-2 mL; the ultrasonic power is 50-100 W, the ultrasonic time is 3-5 min; the thickness of the quartz plate used is 0.5 mm.
  • step (4) the dielectric barrier discharge power, processing time and gas flow are changed, the dielectric barrier discharge power is 100-150W; the reaction gas is argon, ammonia or hydrogen, and the processing time is 5 -15min, the gas flow rate is 200-300mL/min.
  • the method of the present invention prepares a black bismuth tungstate photocatalytic material.
  • the invention adopts a dielectric barrier discharge plasma treatment method, has the characteristics of mild treatment conditions, short reaction time, low energy consumption, and environmental friendliness, is suitable for mass production, and has certain application prospects.
  • the surface of the black bismuth tungstate photocatalyst prepared by the invention contains bismuth element, which promotes the separation of photo-generated holes and electrons, and at the same time has higher visible light absorption, and has certain application prospects in the aspect of photocatalytic CO 2 reduction.
  • FIG. 1 is a color comparison diagram of bismuth tungstate before and after plasma treatment in Example 1.
  • FIG. 1 is a color comparison diagram of bismuth tungstate before and after plasma treatment in Example 1.
  • FIG. 2 shows the XRD patterns of bismuth tungstate before and after plasma treatment in Example 1.
  • FIG. 3 is the ultraviolet-visible diffuse reflection spectrum of bismuth tungstate before and after plasma treatment in Example 1.
  • Example 4 is a comparison diagram of CO 2 reduction activity of bismuth tungstate before and after plasma treatment in Example 1.
  • Example 1 Weigh 10 mg of white bismuth tungstate and add 2 mL of absolute ethanol to ultrasonic treatment, the ultrasonic power is 150 W, and the ultrasonic time is 8 min. Then, the mixed solution was evenly coated on a quartz wafer with a thickness of 0.5mm. After it was completely dried, it was put into a dielectric barrier reactor for the first treatment. The reactor was fed with hydrogen at a constant rate of 150mL/min, and the discharge power was 80W. , The processing time is 5min. After the treatment, the bismuth tungstate was collected again and dispersed again with 2 mL of absolute ethanol, the ultrasonic power was 100 W, the ultrasonic time was 5 min, and the mixed solution was uniformly coated on the quartz plate. Put the completely dried quartz chip into a dielectric barrier reactor for the second treatment. The reactor is fed with 300 mL/min hydrogen at a constant speed, the discharge power is 120W, and the treatment time is 10min, to obtain black bismuth tungstate.
  • Example 2 Weigh 5 mg of white bismuth tungstate and add 2 mL of absolute ethanol to ultrasonic treatment, the ultrasonic power is 100 W, and the ultrasonic time is 5 min. Then, the mixed solution was evenly coated on a quartz wafer with a thickness of 0.5 mm. After it was completely dried, it was put into a dielectric barrier reactor for the first treatment. The reactor was fed with argon gas at a uniform rate of 100 mL/min, and the discharge power was 50W, the processing time is 3min.
  • the bismuth tungstate was collected again and dispersed again with 2 mL of absolute ethanol, the ultrasonic power was 50 W, and the ultrasonic time was 3 min, and the mixed solution was uniformly coated on the quartz plate.
  • the completely dried quartz chip into a dielectric barrier reactor for the second treatment.
  • 300mL/min of argon gas is introduced at a constant speed, the discharge power is 100W, and the treatment time is 5min to obtain black bismuth tungstate. .
  • Example 3 Weigh 20 mg of white bismuth tungstate and add 4 mL of absolute ethanol to ultrasonic treatment, the ultrasonic power is 150 W, and the ultrasonic time is 10 min. Then, the mixed solution was evenly coated on a quartz wafer with a thickness of 0.5 mm. After it was completely dried, it was put into a dielectric barrier reactor for the first treatment. The reactor was fed with 200 mL/min of ammonia at a uniform rate, and the discharge power was 100W, processing time is 5min. After the treatment, the bismuth tungstate was collected again and dispersed again with 2 mL of absolute ethanol, the ultrasonic power was 100 W, the ultrasonic time was 5 min, and the mixed solution was uniformly coated on the quartz plate.
  • Figure 1 is a color comparison diagram of white bismuth tungstate and black bismuth tungstate before and after plasma treatment in Example 1. We can see that the color of bismuth tungstate changed from white to black after treatment.
  • the structure test of the prepared sample was carried out on the German Bruker D8 ray diffractometer (XRD) (Cu-K ⁇ ray, The range is 10°-80°), and the scan rate is 7°min -1 .
  • XRD German Bruker D8 ray diffractometer
  • Figure 2 in Example 1, the black bismuth tungstate before and after the treatment is compared with the white bismuth tungstate. Except for the corresponding peaks of bismuth tungstate, the other peaks all point to the peaks of the bismuth element, indicating that the plasma treatment of bismuth The simple substance is restored.
  • Figure 3 shows the ultraviolet-visible diffuse reflectance spectra of white bismuth tungstate and black bismuth tungstate before and after plasma treatment in Example 1. We can see that the light absorption range of black bismuth tungstate is significantly expanded.
  • Example 4 Weigh 10 mg of the catalyst prepared in Example 1, and dissolve it in the prepared solution (6 mL acetonitrile, 4 mL H 2 O, 2 mL TEOA) by ultrasound for 10 minutes.
  • the reaction system is at a temperature of 10°C and a pressure of 0.75 MPa, 300W xenon lamp (PLS-SXE 300C (BF), Perfectlight) under irradiation.
  • GC-2002 gas chromatography system and thermal conductivity detector produced by Shanghai Kechuang Chromatography Instrument Co., Ltd. were used for gas product analysis.
  • Photocatalytic activity test The photocatalytic CO 2 reduction performance test of the synthesized sample was carried out in a photocatalytic CO 2 reduction reaction instrument model Labsolar-6A produced by PerfectLight.
  • Figure 4 is a comparison diagram of the rate of photocatalytic CO 2 reduction to CO. It can be seen from the figure that the performance of black bismuth tungstate is greatly improved compared with untreated white bismuth tungstate.

Abstract

A preparation method for a black bismuth tungstate photocatalyst. Dielectric barrier discharge is used to generate plasma under different atmospheres so as to treat white bismuth tungstate to obtain a black bismuth tungstate photocatalyst. A bismuth elementary substance is obtained by means of reduction on the surface of bismuth tungstate by means of plasma treatment. Separation between photo-generated holes and electrons is promoted; furthermore, the light absorption range is widened and the photocatalytic CO2 reduction capability is improved.

Description

一种黑色钨酸铋光催化剂及制备方法和应用Black bismuth tungstate photocatalyst and preparation method and application 技术领域Technical field
本发明涉及一种黑色钨酸铋光催化剂的制备方法，属于光催化材料的制备方法技术领域，具体应用方向为光催化CO 2还原。 The invention relates to a preparation method of a black bismuth tungstate photocatalyst, belonging to the technical field of preparation methods of photocatalytic materials, and the specific application direction is photocatalytic CO 2 reduction.
背景技术Background technique
钨酸铋(Bi 2WO 6)作为一种具有一定可见光响应的光催化剂在有机污染物降解以及CO 2还原等方面得到广泛的研究和应用。但是由于传统的钨酸铋催化剂的载流子复合速率高而影响其光催化效率。因此，对于传统钨酸铋催化剂的改性来提高其光催化效率变得越来越重要。现有的光催化剂改性方法主要有形貌调控、贵金属沉积、半导体复合和缺陷调控等。近年来出现的利用等离子体对光催化剂进行表面改性可以大大提高催化性能。 Bismuth tungstate (Bi 2 WO 6 ), as a photocatalyst with a certain visible light response, has been widely studied and applied in the degradation of organic pollutants and CO 2 reduction. However, the high carrier recombination rate of the traditional bismuth tungstate catalyst affects its photocatalytic efficiency. Therefore, the modification of the traditional bismuth tungstate catalyst to improve its photocatalytic efficiency becomes more and more important. The existing photocatalyst modification methods mainly include morphology control, precious metal deposition, semiconductor recombination and defect control. In recent years, the use of plasma to modify the surface of the photocatalyst can greatly improve the catalytic performance.
等离子体指部分或完全电离的气体，且自由电子和离子所带正、负电荷的总和完全抵消，宏观上呈现电中性。根据等离子体的温度可以划分成高温等离子体(热核聚变等离子)和低温等离子体。低温等离子体又包括热等离子体(等离子体弧、等离子体炬等)和冷等离子体(低气压交直流、射频、微波等离子体以及高气压介质阻挡放电、电晕放电、RF放电等)。低温冷等离子体中存在着大量的活性粒子，能够和所接触的材料表面发生反应，因此它们被用来对材料表面进行改性处理.。Plasma refers to a gas that is partially or completely ionized, and the sum of the positive and negative charges carried by free electrons and ions completely cancels out, showing electrical neutrality on a macroscopic scale. According to the temperature of the plasma, it can be divided into high-temperature plasma (thermonuclear fusion plasma) and low-temperature plasma. Low-temperature plasma includes thermal plasma (plasma arc, plasma torch, etc.) and cold plasma (low-pressure AC and DC, radio frequency, microwave plasma, high-pressure dielectric barrier discharge, corona discharge, RF discharge, etc.). There are a large number of active particles in the low-temperature cold plasma, which can react with the surface of the material in contact, so they are used to modify the surface of the material.
介质阻挡放电(DBD)是有绝缘介质***放电空间的一种非平衡态气体放电又称介质阻挡电晕放电或无声放电。介质阻挡放电能够在高气压和很宽的频率范围内工作，通常能够在常压下产生等离子体，电源频率可从50Hz至1M Hz。介质阻挡放电等离子体处理光催化剂具有处理条件温和、反应时间短、能耗低等特点。Dielectric barrier discharge (DBD) is a non-equilibrium gas discharge with an insulating medium inserted into the discharge space, also known as dielectric barrier corona discharge or silent discharge. Dielectric barrier discharge can work at high pressure and a wide frequency range, and can usually generate plasma under normal pressure. The power frequency can range from 50 Hz to 1 MHz. Dielectric barrier discharge plasma processing photocatalyst has the characteristics of mild processing conditions, short reaction time, and low energy consumption.
发明内容Summary of the invention
本发明的目的是针对传统钨酸铋光催化材料可见光利用率低的缺点，利用介质阻挡放电，在不同气氛下产生等离子体，对白色钨酸铋进行处理，得到黑色钨酸铋光催化剂，等离子体处理使得钨酸铋表面还原出铋单质，促进了光生空穴和电子的分离，同时拓宽了光吸收范围，提高了光催化CO 2还原能力。 The purpose of the present invention is to address the disadvantages of low visible light utilization of traditional bismuth tungstate photocatalyst materials, use dielectric barrier discharge to generate plasma in different atmospheres, and process white bismuth tungstate to obtain black bismuth tungstate photocatalyst, plasma The bulk treatment reduces the bismuth element on the surface of the bismuth tungstate, promotes the separation of photogenerated holes and electrons, broadens the light absorption range, and improves the photocatalytic CO 2 reduction ability.
为实现上述发明目的，主要采用以下技术方案：In order to achieve the above-mentioned purpose of the invention, the following technical solutions are mainly adopted:
一种黑色钨酸铋光催化剂的制备方法，包括如下步骤：A preparation method of black bismuth tungstate photocatalyst includes the following steps:
(1)称取白色钨酸铋和无水乙醇经超声分散，形成均匀混合物，将混合物均匀涂敷在石英片上，然后进行烘干；(1) Weigh white bismuth tungstate and absolute ethanol and disperse ultrasonically to form a homogeneous mixture, uniformly coat the mixture on the quartz plate, and then dry;
(2)将烘干的带有白色钨酸铋的石英片放置于介质阻挡放电反应器中，以一定的功率和时间进行等离子体放电处理，处理过程中匀速通入反应气体；(2) Place the dried quartz plate with white bismuth tungstate in a dielectric barrier discharge reactor, perform plasma discharge treatment with a certain power and time, and pass in the reaction gas at a uniform speed during the treatment;
(3)将第一次等离子体处理过后的钨酸铋收集起来用无水乙醇重新超声分散，形成均匀混合物，将混合物均匀涂敷在石英片上，然后进行烘干；(3) Collect the bismuth tungstate after the first plasma treatment and re-disperse it ultrasonically with absolute ethanol to form a homogeneous mixture. The mixture is evenly coated on the quartz plate, and then dried;
(4)将完全烘干的带有钨酸铋的石英片放置于介质阻挡放电反应器中进行二次处理，处理过程中匀速通入反应气体，处理结束最终得到黑色钨酸铋光催化材料。(4) The completely dried quartz plate with bismuth tungstate is placed in a dielectric barrier discharge reactor for secondary treatment. During the treatment process, the reaction gas is introduced at a constant speed. After the treatment, the black bismuth tungstate photocatalytic material is finally obtained.
上述制备方法中：步骤(1)中，所述的白色钨酸铋用量为5-20mg；无水乙醇用量为2-4mL；超声功率为100-150W，超声时间为5-10min；所用石英片厚度为0.5mm。In the above preparation method: in step (1), the amount of white bismuth tungstate is 5-20mg; the amount of absolute ethanol is 2-4mL; the ultrasonic power is 100-150W, the ultrasonic time is 5-10min; the quartz plate used The thickness is 0.5mm.
上述制备方法中：步骤(2)中，所述的介质阻挡放电功率为50-100W；反应气体为氩气、氨气或氢气，处理时间为1-5min，气体流量为100-200mL/min。In the above preparation method: in step (2), the dielectric barrier discharge power is 50-100 W; the reaction gas is argon, ammonia or hydrogen, the treatment time is 1-5 min, and the gas flow rate is 100-200 mL/min.
上述制备方法中：步骤(3)中，所述的无水乙醇用量为1-2mL；超声功率为50-100W，超声时间为3-5min；所用石英片厚度为0.5mm。In the above preparation method: in step (3), the amount of the absolute ethanol is 1-2 mL; the ultrasonic power is 50-100 W, the ultrasonic time is 3-5 min; the thickness of the quartz plate used is 0.5 mm.
上述制备方法中：步骤(4)中，改变介质阻挡放电功率、处理时间和气体流量，所述的介质阻挡放电功率为100-150W；反应气体为氩气、氨气或氢气，处理时间为5-15min，气体流量为200-300mL/min。In the above preparation method: in step (4), the dielectric barrier discharge power, processing time and gas flow are changed, the dielectric barrier discharge power is 100-150W; the reaction gas is argon, ammonia or hydrogen, and the processing time is 5 -15min, the gas flow rate is 200-300mL/min.
本发明所述方法，制备得到了黑色钨酸铋光催化材料。The method of the present invention prepares a black bismuth tungstate photocatalytic material.
本发明有益效果在于：The beneficial effects of the present invention are:
本发明采用介质阻挡放电等离子体处理法，具有处理条件温和、反应时间短、能耗低、环境友好的特点，适用于大批量生产，有一定的应用前景。The invention adopts a dielectric barrier discharge plasma treatment method, has the characteristics of mild treatment conditions, short reaction time, low energy consumption, and environmental friendliness, is suitable for mass production, and has certain application prospects.
本发明制备得到的黑色钨酸铋光催化剂表面含有铋单质，促进了光生空穴和电子的分离，同时有较高的可见光吸收，在光催化CO 2还原方面有一定的应用前景。 The surface of the black bismuth tungstate photocatalyst prepared by the invention contains bismuth element, which promotes the separation of photo-generated holes and electrons, and at the same time has higher visible light absorption, and has certain application prospects in the aspect of photocatalytic CO 2 reduction.
附图说明Description of the drawings
图1为实施例1中等离子体处理前后钨酸铋的颜色对比图。FIG. 1 is a color comparison diagram of bismuth tungstate before and after plasma treatment in Example 1. FIG.
图2为实施例1中等离子体处理前后钨酸铋的XRD图谱。2 shows the XRD patterns of bismuth tungstate before and after plasma treatment in Example 1. FIG.
图3为实施例1中等离子体处理前后钨酸铋的紫外-可见光漫反射图谱。3 is the ultraviolet-visible diffuse reflection spectrum of bismuth tungstate before and after plasma treatment in Example 1. FIG.
图4为实施例1中等离子体处理前后钨酸铋的CO 2还原活性对比图。 4 is a comparison diagram of CO 2 reduction activity of bismuth tungstate before and after plasma treatment in Example 1.
具体实施方式detailed description
以下结合具体实施方式对本发明进行详细阐述，而不是限制本发明The following describes the present invention in detail with reference to specific embodiments, rather than limiting the present invention
下述实施例中使用的实验方法如无特殊说明，均为常规方法。The experimental methods used in the following examples are conventional methods unless otherwise specified.
下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。The materials, reagents, etc. used in the following examples can be obtained from commercial sources unless otherwise specified.
实施例1：称取10mg白色钨酸铋加入2mL无水乙醇中超声处理，超声功率为150W，超声时间8min。然后，将混合溶液均匀涂敷在厚度0.5mm石英片上，在完全烘干后，放入介质阻挡反应器中进行第一次处理，反应器中匀速通入150mL/min的氢气，放电功率为80W，处理时间为5min。将处理后钨酸铋重新收集用2mL无水乙醇重新超声分散，超声功率为100W，超声时间5min，将混合液均匀涂敷在石英片上。将完全烘干的石英片，放入介质阻挡反应器中进行第二次处理，反应器中匀速通入300mL/min的氢气，放电功率为120W，处理时间为10min，即得到黑色钨酸铋。Example 1: Weigh 10 mg of white bismuth tungstate and add 2 mL of absolute ethanol to ultrasonic treatment, the ultrasonic power is 150 W, and the ultrasonic time is 8 min. Then, the mixed solution was evenly coated on a quartz wafer with a thickness of 0.5mm. After it was completely dried, it was put into a dielectric barrier reactor for the first treatment. The reactor was fed with hydrogen at a constant rate of 150mL/min, and the discharge power was 80W. , The processing time is 5min. After the treatment, the bismuth tungstate was collected again and dispersed again with 2 mL of absolute ethanol, the ultrasonic power was 100 W, the ultrasonic time was 5 min, and the mixed solution was uniformly coated on the quartz plate. Put the completely dried quartz chip into a dielectric barrier reactor for the second treatment. The reactor is fed with 300 mL/min hydrogen at a constant speed, the discharge power is 120W, and the treatment time is 10min, to obtain black bismuth tungstate.
实施例2：称取5mg白色钨酸铋加入2mL无水乙醇中超声处理，超声功率为100W，超声时间5min。然后，将混合溶液均匀涂敷在厚度0.5mm石英片上，在完全烘干后，放入介质阻挡反应器中进行第一次处理，反应器中匀速通入100mL/min的氩气，放电功率为50W，处理时间为3min。将处理后钨酸铋重新收集用2mL无水乙醇重新超声分散，超声功率为50W，超声时间3min，将混合液均匀涂敷在石英片上。将完全烘干的石英片，放入介质阻挡反应器中进行第二次处理，反应器中匀速通入300mL/min的氩气，放电功率为100W，处理时间为5min，即得到黑色钨酸铋。Example 2: Weigh 5 mg of white bismuth tungstate and add 2 mL of absolute ethanol to ultrasonic treatment, the ultrasonic power is 100 W, and the ultrasonic time is 5 min. Then, the mixed solution was evenly coated on a quartz wafer with a thickness of 0.5 mm. After it was completely dried, it was put into a dielectric barrier reactor for the first treatment. The reactor was fed with argon gas at a uniform rate of 100 mL/min, and the discharge power was 50W, the processing time is 3min. After the treatment, the bismuth tungstate was collected again and dispersed again with 2 mL of absolute ethanol, the ultrasonic power was 50 W, and the ultrasonic time was 3 min, and the mixed solution was uniformly coated on the quartz plate. Put the completely dried quartz chip into a dielectric barrier reactor for the second treatment. Into the reactor, 300mL/min of argon gas is introduced at a constant speed, the discharge power is 100W, and the treatment time is 5min to obtain black bismuth tungstate. .
实施例3：称取20mg白色钨酸铋加入4mL无水乙醇中超声处理，超声功率为150W，超声时间10min。然后，将混合溶液均匀涂敷在厚度0.5mm石英片上，在完全烘干后，放入介质阻挡反应器中进行第一次处理，反应器中匀速通入200mL/min的氨气，放电功率为100W，处理时间为5min。将处理后钨酸铋重新收集用2mL无水乙醇重新超声分散，超声功率为100W，超声时间5min，将混合液均匀涂敷在石英片上。将完全烘干的石英片，放入介质阻挡反应器中进行第二次处理，反应器中匀速通入300mL/min的氨气，放电功率为150W，处理时间为15min，即得到黑色钨酸铋。Example 3: Weigh 20 mg of white bismuth tungstate and add 4 mL of absolute ethanol to ultrasonic treatment, the ultrasonic power is 150 W, and the ultrasonic time is 10 min. Then, the mixed solution was evenly coated on a quartz wafer with a thickness of 0.5 mm. After it was completely dried, it was put into a dielectric barrier reactor for the first treatment. The reactor was fed with 200 mL/min of ammonia at a uniform rate, and the discharge power was 100W, processing time is 5min. After the treatment, the bismuth tungstate was collected again and dispersed again with 2 mL of absolute ethanol, the ultrasonic power was 100 W, the ultrasonic time was 5 min, and the mixed solution was uniformly coated on the quartz plate. Put the completely dried quartz chip into a dielectric barrier reactor for the second treatment. Ammonia gas of 300mL/min is introduced into the reactor at a constant speed, the discharge power is 150W, and the treatment time is 15min, then black bismuth tungstate is obtained. .
图1为实施例1中，等离子体处理前后，白色钨酸铋和黑色钨酸铋的颜色对比图，我们可以看出处理后，钨酸铋颜色由白色变为黑色。Figure 1 is a color comparison diagram of white bismuth tungstate and black bismuth tungstate before and after plasma treatment in Example 1. We can see that the color of bismuth tungstate changed from white to black after treatment.
制备的样品的结构测试是在德国Bruker D8型射线衍射仪(XRD)上进行的(Cu-Kα射线，
Figure PCTCN2020114816-appb-000001
范围是10°-80°)，扫描速率为7°min -1。如图2所示，实施例1中，处理前后黑色钨酸铋与白色钨酸铋相比，除了钨酸铋对应峰外，出现的其他峰均指向铋单质所属峰，表明经等离子体处理铋单质被还原出来。 The structure test of the prepared sample was carried out on the German Bruker D8 ray diffractometer (XRD) (Cu-Kα ray,
Figure PCTCN2020114816-appb-000001
The range is 10°-80°), and the scan rate is 7°min -1 . As shown in Figure 2, in Example 1, the black bismuth tungstate before and after the treatment is compared with the white bismuth tungstate. Except for the corresponding peaks of bismuth tungstate, the other peaks all point to the peaks of the bismuth element, indicating that the plasma treatment of bismuth The simple substance is restored.
图3为实施例1中，等离子体处理前后，白色钨酸铋和黑色钨酸铋的紫外-可见漫反射光谱，我们可以看出，黑色钨酸铋的吸光范围明显扩展。Figure 3 shows the ultraviolet-visible diffuse reflectance spectra of white bismuth tungstate and black bismuth tungstate before and after plasma treatment in Example 1. We can see that the light absorption range of black bismuth tungstate is significantly expanded.
实施例4：称取10mg实施例1所制备的催化剂，通过超声10分钟溶于配好的溶液中(6mL乙腈，4mL H 2O，2mL TEOA)，反应体系在温度为10℃，压强为0.75MPa，300W氙灯(PLS-SXE 300C(BF)，Perfectlight)下照射进行。用上海科创色谱仪器有限公司生产的GC-2002气相色谱***和热导检测器进行气体产物分析。 Example 4: Weigh 10 mg of the catalyst prepared in Example 1, and dissolve it in the prepared solution (6 mL acetonitrile, 4 mL H 2 O, 2 mL TEOA) by ultrasound for 10 minutes. The reaction system is at a temperature of 10°C and a pressure of 0.75 MPa, 300W xenon lamp (PLS-SXE 300C (BF), Perfectlight) under irradiation. GC-2002 gas chromatography system and thermal conductivity detector produced by Shanghai Kechuang Chromatography Instrument Co., Ltd. were used for gas product analysis.
光催化活性测试：在PerfectLight公司生产的型号为Labsolar-6A的光催化CO 2还原反应仪器中进行合成样品的光催化CO 2还原性能测试。图4为光催化CO 2还原生成CO速率对比图，从图中可以看出制备的黑色钨酸铋和未经处理的白色钨酸铋相比，黑色钨酸铋性能有很大的提升。 Photocatalytic activity test: The photocatalytic CO 2 reduction performance test of the synthesized sample was carried out in a photocatalytic CO 2 reduction reaction instrument model Labsolar-6A produced by PerfectLight. Figure 4 is a comparison diagram of the rate of photocatalytic CO 2 reduction to CO. It can be seen from the figure that the performance of black bismuth tungstate is greatly improved compared with untreated white bismuth tungstate.
以上所揭露的仅为本发明较佳实例而已，再不脱离本发明上述方法思想的情况下，根据本领域普通技术知识和惯用手段进行替换和改进，均应包含在本发明保护范围之内。The above-disclosed are only preferred examples of the present invention. Without departing from the above-mentioned method idea of the present invention, replacements and improvements based on common technical knowledge and conventional means in the field should all be included in the protection scope of the present invention.

Claims (5)

  1. 一种黑色钨酸铋光催化剂的制备方法，其特征在于，利用介质阻挡放电，在不同气氛下产生等离子体，对白色钨酸铋进行处理，得到黑色钨酸铋光催化剂，等离子体处理使得钨酸铋表面还原出铋单质，促进了光生空穴和电子的分离，同时拓宽了光吸收范围，提高了光催化CO 2还原能力，具体步骤如下： A preparation method of black bismuth tungstate photocatalyst is characterized in that the dielectric barrier discharge is used to generate plasma in different atmospheres, and white bismuth tungstate is processed to obtain black bismuth tungstate photocatalyst. The plasma treatment makes tungsten Bismuth is reduced on the surface of bismuth acid, which promotes the separation of photo-generated holes and electrons, broadens the light absorption range, and improves the photocatalytic CO 2 reduction ability. The specific steps are as follows:
    (1)称取白色钨酸铋和无水乙醇经超声分散，形成均匀混合物，将混合物均匀涂敷在石英片上，然后进行烘干；(1) Weigh white bismuth tungstate and absolute ethanol and disperse ultrasonically to form a homogeneous mixture, uniformly coat the mixture on the quartz plate, and then dry;
    (2)将烘干的带有白色钨酸铋的石英片放置于介质阻挡放电反应器中，以一定的功率和时间进行等离子体放电处理，处理过程中匀速通入反应气体；(2) Place the dried quartz plate with white bismuth tungstate in a dielectric barrier discharge reactor, perform plasma discharge treatment with a certain power and time, and pass in the reaction gas at a uniform speed during the treatment;
    (3)将第一次等离子体处理过后的钨酸铋收集起来用无水乙醇重新超声分散，形成均匀混合物，将混合物均匀涂敷在石英片上，然后进行烘干；(3) Collect the bismuth tungstate after the first plasma treatment and re-disperse it ultrasonically with absolute ethanol to form a homogeneous mixture. The mixture is evenly coated on the quartz plate, and then dried;
    (4)将完全烘干的带有钨酸铋的石英片放置于介质阻挡放电反应器中进行二次处理，处理过程中匀速通入反应气体，处理结束最终得到黑色钨酸铋光催化材料。(4) The completely dried quartz plate with bismuth tungstate is placed in a dielectric barrier discharge reactor for secondary treatment. During the treatment process, the reaction gas is introduced at a constant speed. After the treatment, the black bismuth tungstate photocatalytic material is finally obtained.
  2. 如权利要求1所述的一种黑色钨酸铋光催化剂的制备方法，其特征在于，步骤(1)中，所述的白色钨酸铋用量为5-20mg；无水乙醇用量为2-4mL；超声功率为100-150W，超声时间为5-10min；所用石英片厚度为0.5mm。The method for preparing a black bismuth tungstate photocatalyst according to claim 1, wherein in step (1), the amount of white bismuth tungstate is 5-20 mg; the amount of anhydrous ethanol is 2-4 mL ; The ultrasonic power is 100-150W, the ultrasonic time is 5-10min; the thickness of the quartz plate used is 0.5mm.
  3. 如权利要求1所述的一种黑色钨酸铋光催化剂的制备方法，其特征在于，步骤(2)中，所述的介质阻挡放电功率为50-100W；反应气体为氩气、氨气或氢气，处理时间为1-5min，气体流量为100-200mL/min。The method for preparing a black bismuth tungstate photocatalyst according to claim 1, wherein in step (2), the dielectric barrier discharge power is 50-100W; the reaction gas is argon, ammonia or For hydrogen, the treatment time is 1-5min, and the gas flow rate is 100-200mL/min.
  4. 如权利要求1所述的一种黑色钨酸铋光催化剂的制备方法，其特征在于，步骤(3)中，所述的无水乙醇用量为1-2mL；超声功率为50-100W，超声时间为3-5min；所用石英片厚度为0.5mm。The method for preparing a black bismuth tungstate photocatalyst according to claim 1, wherein in step (3), the amount of the absolute ethanol is 1-2mL; the ultrasonic power is 50-100W, and the ultrasonic time is 50-100W. It is 3-5min; the thickness of the quartz plate used is 0.5mm.
  5. 如权利要求1所述的一种黑色钨酸铋光催化剂的制备方法，其特征在于，步骤(4)中，改变介质阻挡放电功率、处理时间和气体流量，所述的介质阻挡放电功率为100-150W；反应气体为氩气、氨气或氢气，处理时间为5-15min，气体流量为200-300mL/min。The method for preparing a black bismuth tungstate photocatalyst according to claim 1, wherein in step (4), the dielectric barrier discharge power, processing time and gas flow are changed, and the dielectric barrier discharge power is 100 -150W; the reaction gas is argon, ammonia or hydrogen, the processing time is 5-15min, and the gas flow rate is 200-300mL/min.
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