WO2023023919A1 - Tungsten oxide nanorod/tin ion modified titanium carbide quantum dot/indium sulfide nanosheet composite material, and preparation method therefor and use thereof - Google Patents

Tungsten oxide nanorod/tin ion modified titanium carbide quantum dot/indium sulfide nanosheet composite material, and preparation method therefor and use thereof Download PDF

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WO2023023919A1
WO2023023919A1 PCT/CN2021/114162 CN2021114162W WO2023023919A1 WO 2023023919 A1 WO2023023919 A1 WO 2023023919A1 CN 2021114162 W CN2021114162 W CN 2021114162W WO 2023023919 A1 WO2023023919 A1 WO 2023023919A1
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titanium carbide
carbide quantum
tin
quantum dots
tungsten oxide
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PCT/CN2021/114162
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French (fr)
Chinese (zh)
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路建美
李娜君
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苏州大学
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    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the invention belongs to the technical field of inorganic nanocomposite materials and photocatalysis thereof, and specifically relates to a preparation method of a titanium carbide quantum dot/indium sulfide nanosheet Z-type heterojunction composite material modified by tungsten oxide nanorods/tin ions and its application in visible light.
  • Photocatalytic technology has attracted extensive attention due to its potential application in solving environmental pollution and energy crisis.
  • more and more semiconductor materials are used in the field of catalysis, in which the quantum confinement of quantum dot materials due to their small volume will lead to an expansion of the band gap, making them have better physical and chemical properties. Tonality, more abundant active edge sites, thus gradually showing stronger competitiveness in recent studies.
  • the existing technology uses titanium carbide quantum dots as the electron transfer medium, first uses a mild etching method to prepare a preliminary layered titanium carbide solution, and then efficiently prepares titanium carbide quantum dots through a simple method of multiple freezing and thawing plus ultrasound , and then statically adsorbed to make the quantum dots evenly loaded on the surface of tungsten trioxide nanorods, and finally build a Z-type heterojunction composite material of tungsten oxide nanorods/titanium carbide quantum dots/indium sulfide nanosheets by reflowing indium sulfide nanosheets, Has catalytic activity.
  • the catalytic rate of the catalyst still has room for further improvement.
  • the purpose of the present invention is to provide a tungsten oxide nanorod/tin ion modified titanium carbide quantum dot/indium sulfide nanosheet Z-type heterojunction composite material responsive to visible light and a preparation method thereof.
  • Tin metal ion has high electrical conductivity, low discharge point and environmental friendliness; the new two-dimensional layered compound titanium carbide, as a transition metal carbide, has good metal conductivity, hydrophilicity and abundant active catalytic site.
  • the tin ion-modified titanium carbide quantum dots constructed by the two can replace noble metals as the electron transfer medium in the heterojunction, enhance the electron migration ability, and realize the photocatalytic treatment of pollutants in water and the decomposition of water to produce hydrogen under the irradiation of visible light.
  • the invention firstly prepares titanium carbide quantum dots, then puts divalent tin compounds into the titanium carbide quantum dot aqueous solution, and successfully anchors divalent tin ions on the surface of pre-etched titanium carbide quantum dots through a simple ultrasonic method to obtain tin Ion-modified titanium carbide quantum dots; then disperse the tungsten trioxide nanorods prepared by the hydrothermal method in an aqueous solution containing tin ion-modified titanium carbide quantum dots, stir for a period of time and let stand, after freeze-drying, get loaded tin Tungsten oxide nanorod powder of ion-modified titanium carbide quantum dots; then stir and mix the above powder with indium compound and sulfur compound evenly, and carry out reflux reaction under constant temperature conditions to obtain tungsten oxide nanorods/tin ion-modified titanium carbide quantum dots /Indium sulfide nanosheet Z-type heterojunction nanocomposite material.
  • the invention introduces tin ions into the composite material, which can improve the efficiency of photocatalytic treatment of pollutants and decomposition of water to produce hydrogen.
  • the Z-type heterojunction composite material constructed by the invention can significantly improve the photocatalytic efficiency.
  • titanium carbide quantum dots/indium sulfide composites modified by tungsten trioxide/tin ions are significantly better than tungsten trioxide/titanium carbide quantum dots/ indium sulfide.
  • titanium carbide quantum dots/indium sulfide nanosheet composite material modified by tungsten oxide nanorods/tin ions including titanium carbide quantum dots modified by tungsten oxide nanorods, tin ions and sulfide Indium nanosheets; preferably, composed of tungsten oxide nanorods, tin ion-modified titanium carbide quantum dots and indium sulfide nanosheets.
  • the invention discloses a preparation method of the above tungsten oxide nanorod/tin ion modified titanium carbide quantum dot/indium sulfide nanosheet composite material, comprising the following steps: introducing tin ions into the titanium carbide quantum dot to obtain tin ion modified titanium carbide Quantum dots; then load the titanium carbide quantum dots modified by the tin ions on the oxide nanorods to obtain the tungsten oxide nanorods of the titanium carbide quantum dots modified by the loaded tin ions; then the titanium carbide quantum dots modified by the loaded tin ions Tungsten oxide nanorods, indium compounds and sulfur compounds react in a solvent to obtain a composite material of tungsten oxide nanorods/tin ion-modified titanium carbide quantum dots/indium sulfide nanosheets, which is a Z-type heterojunction composite material.
  • both tungsten oxide nanorods and titanium carbide quantum dots are existing products, prepared with reference to the published patent (CN111974427A);
  • the indium compound is an indium compound such as indium trichloride tetrahydrate and indium nitrate tetrahydrate, preferably Indium trichloride tetrahydrate;
  • the sulfur compound is sodium sulfide nonahydrate, thioacetamide, thiourea and other sulfur compounds, preferably thioacetamide;
  • the solvent is alcohol, preferably ethylene glycol.
  • tin compounds and titanium carbide quantum dots are used as raw materials, and the electropositive divalent tin ions in the tin compounds are electrostatically adsorbed to the electronegative -OH and -F terminal groups on the surface by ultrasonic assistance.
  • the titanium carbide quantum dots modified by tin ions are obtained; the tungsten oxide nanorod powder is dispersed in the aqueous solution containing titanium carbide quantum dots modified by tin ions, stirred for a period of time and then left to stand to obtain the loaded tin ion Tungsten oxide nanorods of modified titanium carbide quantum dots; the tungsten oxide nanorods of titanium carbide quantum dots loaded with tin ions are reacted with indium compounds and sulfur compounds at constant temperature in a solvent to obtain tungsten oxide nanorods/tin ion modified
  • the titanium carbide quantum dot/indium sulfide nanosheet composite material is a Z-type heterojunction material.
  • the tin compound is a water-soluble divalent tin compound, preferably stannous chloride dihydrate; the mass ratio of the tin compound to the titanium carbide quantum dot is 30-50:12, preferably 35-45:12.
  • the ultrasonic power is 400-600 W and the time is 100-150 min.
  • the divalent tin ions participate in the construction of the Z-type heterojunction composite material, which increases the contact between the reactant and the catalytic active site, thereby improving the catalytic efficiency of photocatalysis.
  • the invention discloses the application of the tungsten oxide nanorod/tin ion-modified titanium carbide quantum dot/indium sulfide nanosheet composite material in removing water body pollutants or in photocatalytic hydrogen production.
  • the invention discloses a treatment method for water containing pollutants, which includes the following steps: adding the above-mentioned tungsten oxide nanorod/titanium carbide quantum dot/indium sulfide nanosheet composite material modified by tin ions into the water containing pollutants to complete the process of Water treatment.
  • the above-mentioned tungsten oxide nanorod/tin ion modified titanium carbide quantum dot/indium sulfide nanosheet composite material is added to the water body containing pollutants, and the treatment of the water body containing pollutants is completed under visible light irradiation.
  • the pollutants are heavy metals or organic pollutants, such as hexavalent chromium and bisphenol A.
  • the invention discloses a method for photocatalytic hydrogen production, comprising the following steps of adding the above-mentioned tungsten oxide nanorod/tin ion modified titanium carbide quantum dot/indium sulfide nanosheet composite material and a sacrificial agent into water to complete photocatalytic hydrogen production .
  • the above-mentioned tungsten oxide nanorod/tin ion modified titanium carbide quantum dot/indium sulfide nanosheet composite material is added into water, and photocatalytic hydrogen production is completed under visible light irradiation.
  • the sacrificial agent in the photocatalytic hydrogen production process is sodium sulfide, sodium sulfite, sodium sulfate, etc., preferably sodium sulfide and sodium sulfite.
  • the Z-type heterojunction composite material containing tin ions disclosed by the present invention accelerates the transfer of electrons and enhances the photocatalytic performance; it has strong light absorption capacity in the visible light region, and is a visible light with excellent performance
  • Catalytic materials used to catalyze the removal of pollutants such as hexavalent chromium heavy metal ions and photocatalytic decomposition of water to produce hydrogen; only visible light sources are required to provide light; as specific tungsten oxide nanorods/tin ion-modified titanium carbide quantum dots/indium sulfide nanosheets In the photocatalytic water splitting hydrogen production experiment of composite materials, with the prolongation of the light time, the hydrogen production increased.
  • the hydrogen production was 75 micromol/g.
  • indium sulfide and non-tin ion modified The quantum dot-based tungsten oxide nanorods/titanium carbide quantum dots/indium sulfide nanosheet composites were illuminated for 5 h, and the hydrogen production was 10.7 micromol/g and 12.3 micromol/g.
  • the removal rate of tungsten oxide nanorods/tin ion-modified titanium carbide quantum dots/indium sulfide nanosheet Z-type heterojunction for hexavalent chromium in water is faster than that of the unmodified tungsten oxide nanorods/titanium carbide quantum dots/ 2.1 times that of indium sulfide nanosheet composites.
  • the Z-type heterojunction raw material of the tin ion-modified titanium carbide quantum dot disclosed by the invention is cheap and easy to obtain, and the preparation method is simple, which is beneficial to its further popularization and use.
  • Figure 1 is a transmission electron microscope image of tin ion-modified titanium carbide quantum dots.
  • Fig. 2 is an X-ray photoelectron energy spectrum diagram of tin ion-modified titanium carbide quantum dots and titanium carbide quantum dots.
  • Fig. 3 is a scanning electron microscope image of a Z-type heterojunction of tungsten oxide nanorods/tin ion-modified titanium carbide quantum dots/indium oxide nanosheets.
  • Figure 4 shows the Z-type heterojunction of tungsten oxide nanorods/titanium carbide quantum dots/indium oxide nanosheets modified by tin ions, the Z-type heterojunction of tungsten oxide nanorods/titanium carbide quantum dots/indium oxide nanosheets, and tungsten trioxide and indium sulfide photocatalytic hydrogen production rate diagram.
  • Figure 5 shows the effect of tungsten oxide nanorods/titanium carbide quantum dots/indium oxide nanosheets Z-type heterojunction and tungsten oxide nanorods/titanium carbide quantum dots/indium oxide nanosheets Z-type heterojunction in water respectively.
  • a Z-type heterojunction of titanium carbide quantum dots modified with tin ions is constructed by combining simple ultrasonic method, hydrothermal method, reflux method and other preparation methods for the treatment of water body pollutants and photocatalytic decomposition of water to produce hydrogen.
  • titanium carbide quantum dots decorated with tin ions have good metal-like conductivity and are good dielectric materials.
  • the preparation method of the tungsten oxide nanorod/tin ion modified titanium carbide quantum dot/indium sulfide nanosheet Z-type heterojunction composite material of the present invention is as follows: firstly, referring to the published patent (CN111974427A) to prepare titanium carbide quantum dots with negative ions on the surface ; Then, the electrostatic adsorption of electropositive divalent tin ions in the tin compound is anchored around the titanium carbide quantum dots with electronegative -OH and -F end groups on the surface by ultrasonic assistance, to obtain tin ion modification Titanium carbide quantum dots; then place the tungsten trioxide nanorods prepared with reference to the published patent (CN111974427A) in the aqueous solution of the quantum dots, stir and leave to stand to obtain tungsten oxide nanorods loaded with tin ion-modified quantum dots ; The indium compound, the sulfur compound, and the tungsten oxide nanorods loaded with quantum dots are refluxed to obtain tungs
  • the raw materials involved in the present invention are all commercially available conventional products, and the specific operation methods and testing methods are all conventional methods in this field. If temperature and gas environment are not particularly pointed out, they are all carried out at room temperature and conventional environment.
  • Example 1 Preparation of titanium carbide quantum dots modified by tin ions: Take 120 mL of titanium carbide quantum dot aqueous solution (100 mg/L) prepared with reference to the published patent (CN111974427A Example 1) and place it in a reaction eggplant-shaped bottle, then add 40 mg of stannous chloride dihydrate, and then use a vacuum pump to extract the air in the eggplant-shaped bottle to make the environment in the eggplant-shaped bottle a vacuum, then seal the eggplant-shaped bottle with a sealing strip, and then ultrasonicate at 600 W for 2 h at room temperature , to obtain a tin ion-modified titanium carbide quantum dot solution, which is used in Example 2.
  • Accompanying drawing 1 is the TEM image of the titanium carbide quantum dot obtained above, it can be clearly seen from the above figure that the titanium carbide quantum dot modified by tin ions has a single size and is uniformly dispersed.
  • Accompanying drawing 2 is the X-ray photoelectron energy spectrogram of the titanium carbide quantum dot modified by tin ions obtained above, as can be seen from the figure, compared with the unmodified quantum dot, the modified titanium carbide quantum dot has obvious tin The peaks of the ions appear, proving that the tin ions are successfully decorated around the titanium carbide quantum dots.
  • the specific steps are as follows: take 0.1 g of tungsten trioxide nanorod powder prepared with reference to the published patent (CN111974427A embodiment two) and add it to the titanium carbide quantum dot aqueous solution modified by tin ions in the above embodiment one, and stir in a vacuum environment (1000 rpm) for 12 h at room temperature for 12 h, and then freeze-dried in a lyophilizer to obtain tungsten trioxide nanorod powders loaded with tin ion-modified titanium carbide quantum dots.
  • the specific steps are as follows: Take 10 mg of the above obtained tungsten oxide nanorods/tin ion-modified titanium carbide quantum dots/indium sulfide nanosheet Z-type heterocomposite material, put it in 10 mL containing 0.1 mol/L sodium sulfide and 0.1 mol /L of sodium sulfite aqueous solution.
  • a 300 W xenon lamp was used as the light source, and a closed photocatalytic reactor was used as the reaction vessel, and 5 mL of gas in the photocatalytic reactor was extracted every 1 h with a syringe. 5 mL of gas components were intermittently extracted and injected into a gas chromatograph with a thermal conductivity detector. The amount of hydrogen produced was calculated using a calibration curve of hydrogen moles versus peak area.
  • indium sulfide (comparative example 1) and tungsten oxide nanorods/titanium carbide quantum dots/indium sulfide nanorods without tin ion-modified quantum dots
  • the hydrogen production was 10.7 micromol/g and 12.3 micromol/g respectively
  • tungsten trioxide (CN111974427A Example 2) did not produce hydrogen under light conditions. Pure titanium carbide quantum dots have no catalytic effect and cannot photocatalyze hydrogen production.
  • Example 4 The photocatalytic reduction experiment of tungsten oxide nanorods/titanium carbide quantum dots/indium sulfide nanosheets Z-type heterojunction pair in water.
  • the specific steps are as follows: take 5 mg of the tungsten oxide nanorods/tin ion-modified titanium carbide quantum dots/indium sulfide nanosheet Z-type heterogeneous composite material obtained above, and place it in 20 mL of dichromic acid with a concentration of 10 mg/L. Potassium aqueous solution (hexavalent chromium ion concentration is 20 mg/L). Adsorption was carried out for 60 min in the dark to reach adsorption equilibrium.
  • the tungsten oxide nanorods/ The removal rate of hexavalent chromium in the water body where the titanium carbide quantum dots/indium sulfide nanosheet Z-type heterojunction decorated with tin ions can reach 68%; when the visible light is irradiated for 60 s, the removal rate of hexavalent chromium in the water body increases to 77%.
  • the removal rate of tungsten oxide nanorods/tin ion-modified titanium carbide quantum dots/indium sulfide nanosheet Z-type heterojunction for hexavalent chromium in water is faster than that of the unmodified tungsten oxide nanorods/titanium carbide quantum dots/ 2.1 times that of indium sulfide nanosheet composites.
  • Pure titanium carbide quantum dots have no catalytic effect and cannot catalyze the reduction of hexavalent chromium.
  • the tin ions used in the present invention combine tin ions with titanium carbide quantum dots as an electron transfer medium, and the main body is titanium carbide quantum dots.
  • Point, tin plays a role in promoting.
  • the invention first prepares titanium carbide quantum dots, and then uses electrostatic adsorption to anchor electropositive tin ions around the titanium carbide quantum dots with -OH and -F end groups on the surface to prepare tin ion-modified titanium carbide quantum dots.
  • the TiC quantum dots modified by tin ions are evenly loaded on the surface of tungsten trioxide nanorods through electrostatic adsorption and self-assembly, and finally the tungsten oxide nanorods/titanium carbide modified by tin ions are constructed by reflow growth of indium sulfide nanosheets Quantum dot/indium sulfide nanosheet Z-type heterojunction composite material; the obtained composite material can accelerate the transfer of photogenerated electrons, and at the same time solve the problem that nanoscale quantum dots are easy to agglomerate, greatly improving the utilization rate of photogenerated electrons.

Abstract

Disclosed in the present invention are a tungsten oxide nanorod/tin ion modified titanium carbide quantum dot/indium sulfide nanosheet composite material and a preparation method therefor. In the present invention, tin ions are introduced into the composite material, so that the efficiency of photocatalytic reduction of hexavalent chromium in water and decomposition of water to produce hydrogen can be improved. Compared with the tungsten trioxide/titanium carbide quantum dot/indium sulfide composite material introduced with titanium carbide quantum dots which are not modified by tin ions, the Z-type heterojunction composite material constructed by means of the present invention can significantly improve the photocatalytic efficiency. Experiments prove that the performance of the tungsten trioxide/tin ion modified titanium carbide quantum dot/indium sulfide composite material for respectively rapidly reducing hexavalent chromium in water and decomposing water to produce hydrogen under visible light is significantly better than that of tungsten trioxide/titanium carbide quantum dot/indium sulfide. After 6 minutes of irradiation under visible light, hexavalent chromium is completely reduced and removed from water where the Z-type heterojunction of tungsten oxide nanorod/tin ion modified titanium carbide quantum dot/indium sulfide nanosheet is located.

Description

氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片复合材料及其制备方法与应用Tungsten oxide nanorod/tin ion modified titanium carbide quantum dot/indium sulfide nanosheet composite material and its preparation method and application 技术领域technical field
本发明属于无机纳米复合材料及其光催化技术领域，具体涉及一种氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片Z型异质结复合材料的制备方法及其在可见光条件下有效去除水体中污染物和光催化分解水产氢的应用。The invention belongs to the technical field of inorganic nanocomposite materials and photocatalysis thereof, and specifically relates to a preparation method of a titanium carbide quantum dot/indium sulfide nanosheet Z-type heterojunction composite material modified by tungsten oxide nanorods/tin ions and its application in visible light. The application of effective removal of pollutants in water bodies and photocatalytic decomposition of water to produce hydrogen under certain conditions.
背景技术Background technique
光催化技术因其在解决环境污染与能源危机等问题的潜在应用而受到广泛的关注。为了解决日益严重的环境和能源危机，越来越多的半导体材料被应用在催化领域，其中量子点材料由于体积较小产生的量子限制会导致带隙扩大，使其具有更好的理化性质可调性，更丰富的活性边缘位点，从而在近期的研究中逐渐展现出较强的竞争力。现有技术（CN111974427A）以碳化钛量子点为电子传递介质，首先使用温和的刻蚀方法制备初步分层的碳化钛溶液，再通过简单的多次冻融加超声的方法高效制备碳化钛量子点，然后静置吸附使量子点均匀地负载在三氧化钨纳米棒表面，最后通过回流生长硫化铟纳米片构筑氧化钨纳米棒/碳化钛量子点/硫化铟纳米片Z 型异质结复合材料，具有催化活性。不过经过进一步的研究，发现该催化剂的催化速率还有进一步的提升空间。Photocatalytic technology has attracted extensive attention due to its potential application in solving environmental pollution and energy crisis. In order to solve the increasingly serious environmental and energy crisis, more and more semiconductor materials are used in the field of catalysis, in which the quantum confinement of quantum dot materials due to their small volume will lead to an expansion of the band gap, making them have better physical and chemical properties. Tonality, more abundant active edge sites, thus gradually showing stronger competitiveness in recent studies. The existing technology (CN111974427A) uses titanium carbide quantum dots as the electron transfer medium, first uses a mild etching method to prepare a preliminary layered titanium carbide solution, and then efficiently prepares titanium carbide quantum dots through a simple method of multiple freezing and thawing plus ultrasound , and then statically adsorbed to make the quantum dots evenly loaded on the surface of tungsten trioxide nanorods, and finally build a Z-type heterojunction composite material of tungsten oxide nanorods/titanium carbide quantum dots/indium sulfide nanosheets by reflowing indium sulfide nanosheets, Has catalytic activity. However, after further research, it was found that the catalytic rate of the catalyst still has room for further improvement.
技术问题technical problem
本发明的目的是提供一种在可见光响应的氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片Z型异质结复合材料及其制备方法。锡金属离子具有高电导率、较低的放电点位和环境友好性；新型二维层状化合物碳化钛作为一种过渡金属碳化物，具有良好的金属导电性、亲水性和丰富的活性催化位点。二者所构建的锡离子修饰的碳化钛量子点可以代替贵金属作为异质结中的电子传递介质，增强电子迁移能力，在可见光的照射下分别实现光催化处理水体中污染物和分解水产氢。The purpose of the present invention is to provide a tungsten oxide nanorod/tin ion modified titanium carbide quantum dot/indium sulfide nanosheet Z-type heterojunction composite material responsive to visible light and a preparation method thereof. Tin metal ion has high electrical conductivity, low discharge point and environmental friendliness; the new two-dimensional layered compound titanium carbide, as a transition metal carbide, has good metal conductivity, hydrophilicity and abundant active catalytic site. The tin ion-modified titanium carbide quantum dots constructed by the two can replace noble metals as the electron transfer medium in the heterojunction, enhance the electron migration ability, and realize the photocatalytic treatment of pollutants in water and the decomposition of water to produce hydrogen under the irradiation of visible light.
技术解决方案technical solution
本发明首先制备碳化钛量子点，之后在碳化钛量子点水溶液中投入二价锡化合物，通过简单的超声方法将二价锡离子成功锚定在预先刻蚀好的碳化钛量子点表面，得到锡离子修饰的碳化钛量子点；之后将水热法制备的三氧化钨纳米棒分散在含有锡离子修饰的碳化钛量子点水溶液中，搅拌一段时间并静置，经过冻干处理后得到负载有锡离子修饰的碳化钛量子点的氧化钨纳米棒粉末；再将上述粉末与铟化合物和硫化合物搅拌混合均匀，在恒温条件下进行回流反应，得到氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片Z型异质结纳米复合材料。本发明在复合材料中引入锡离子，可以提高光催化处理污染物以及分解水产氢的效率。与引入未进行锡离子修饰的碳化钛量子点的三氧化钨/碳化钛量子点/硫化铟复合材料相比，本发明构建的Z型异质结复合材料能够显著提高光催化效率。实验证实，三氧化钨/锡离子修饰的碳化钛量子点/硫化铟复合材料在可见光下分别还原水体中六价铬和光催化分解水产氢的性能均明显优于三氧化钨/碳化钛量子点/硫化铟。The invention firstly prepares titanium carbide quantum dots, then puts divalent tin compounds into the titanium carbide quantum dot aqueous solution, and successfully anchors divalent tin ions on the surface of pre-etched titanium carbide quantum dots through a simple ultrasonic method to obtain tin Ion-modified titanium carbide quantum dots; then disperse the tungsten trioxide nanorods prepared by the hydrothermal method in an aqueous solution containing tin ion-modified titanium carbide quantum dots, stir for a period of time and let stand, after freeze-drying, get loaded tin Tungsten oxide nanorod powder of ion-modified titanium carbide quantum dots; then stir and mix the above powder with indium compound and sulfur compound evenly, and carry out reflux reaction under constant temperature conditions to obtain tungsten oxide nanorods/tin ion-modified titanium carbide quantum dots /Indium sulfide nanosheet Z-type heterojunction nanocomposite material. The invention introduces tin ions into the composite material, which can improve the efficiency of photocatalytic treatment of pollutants and decomposition of water to produce hydrogen. Compared with the tungsten trioxide/titanium carbide quantum dot/indium sulfide composite material that introduces titanium carbide quantum dots without tin ion modification, the Z-type heterojunction composite material constructed by the invention can significantly improve the photocatalytic efficiency. Experiments have confirmed that titanium carbide quantum dots/indium sulfide composites modified by tungsten trioxide/tin ions are significantly better than tungsten trioxide/titanium carbide quantum dots/ indium sulfide.
为了达到上述目的，本发明采用如下具体技术方案：氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片复合材料，包括氧化钨纳米棒、锡离子修饰的碳化钛量子点以及硫化铟纳米片；优选的，由氧化钨纳米棒、锡离子修饰的碳化钛量子点以及硫化铟纳米片组成。In order to achieve the above object, the present invention adopts the following specific technical solutions: titanium carbide quantum dots/indium sulfide nanosheet composite material modified by tungsten oxide nanorods/tin ions, including titanium carbide quantum dots modified by tungsten oxide nanorods, tin ions and sulfide Indium nanosheets; preferably, composed of tungsten oxide nanorods, tin ion-modified titanium carbide quantum dots and indium sulfide nanosheets.
本发明公开了上述氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片复合材料的制备方法，包括以下步骤：在碳化钛量子点上引入锡离子，得到锡离子修饰的碳化钛量子点；然后在氧化物纳米棒上负载所述锡离子修饰的碳化钛量子点，得到负载锡离子修饰的碳化钛量子点的氧化钨纳米棒；再将负载锡离子修饰的碳化钛量子点的氧化钨纳米棒、铟化合物和硫化合物在溶剂中反应，得到氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片复合材料，为Z型异质结复合材料。The invention discloses a preparation method of the above tungsten oxide nanorod/tin ion modified titanium carbide quantum dot/indium sulfide nanosheet composite material, comprising the following steps: introducing tin ions into the titanium carbide quantum dot to obtain tin ion modified titanium carbide Quantum dots; then load the titanium carbide quantum dots modified by the tin ions on the oxide nanorods to obtain the tungsten oxide nanorods of the titanium carbide quantum dots modified by the loaded tin ions; then the titanium carbide quantum dots modified by the loaded tin ions Tungsten oxide nanorods, indium compounds and sulfur compounds react in a solvent to obtain a composite material of tungsten oxide nanorods/tin ion-modified titanium carbide quantum dots/indium sulfide nanosheets, which is a Z-type heterojunction composite material.
本发明中，氧化钨纳米棒与碳化钛量子点都为现有产品，参照已公开专利（CN111974427A）制备；铟化合物为四水合三氯化铟、四点五水合硝酸铟等铟化合物，优选为四水合三氯化铟；硫化合物为九水合硫化钠、硫代乙酰胺、硫脲等硫化合物，优选为硫代乙酰胺；溶剂为醇，优选乙二醇。In the present invention, both tungsten oxide nanorods and titanium carbide quantum dots are existing products, prepared with reference to the published patent (CN111974427A); the indium compound is an indium compound such as indium trichloride tetrahydrate and indium nitrate tetrahydrate, preferably Indium trichloride tetrahydrate; the sulfur compound is sodium sulfide nonahydrate, thioacetamide, thiourea and other sulfur compounds, preferably thioacetamide; the solvent is alcohol, preferably ethylene glycol.
本发明中，以锡化合物、碳化钛量子点为原料，通过超声辅助将锡化合物中电正性的二价锡离子静电吸附作用锚定在表面带有电负性的-OH和-F末端基团的碳化钛量子点的周围，得到锡离子修饰的碳化钛量子点；将氧化钨纳米棒粉末分散于含有锡离子修饰的碳化钛量子点水溶液中，搅拌一段时间后静置，得到负载锡离子修饰的碳化钛量子点的氧化钨纳米棒；将上述负载锡离子修饰的碳化钛量子点的氧化钨纳米棒与铟化合物、硫化合物在溶剂中恒温回流反应，得到氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片复合材料，为Z型异质结材料。In the present invention, tin compounds and titanium carbide quantum dots are used as raw materials, and the electropositive divalent tin ions in the tin compounds are electrostatically adsorbed to the electronegative -OH and -F terminal groups on the surface by ultrasonic assistance. Around the titanium carbide quantum dots of the cluster, the titanium carbide quantum dots modified by tin ions are obtained; the tungsten oxide nanorod powder is dispersed in the aqueous solution containing titanium carbide quantum dots modified by tin ions, stirred for a period of time and then left to stand to obtain the loaded tin ion Tungsten oxide nanorods of modified titanium carbide quantum dots; the tungsten oxide nanorods of titanium carbide quantum dots loaded with tin ions are reacted with indium compounds and sulfur compounds at constant temperature in a solvent to obtain tungsten oxide nanorods/tin ion modified The titanium carbide quantum dot/indium sulfide nanosheet composite material is a Z-type heterojunction material.
本发明中，锡化合物为水溶性二价锡化合物，优选为氯化亚锡二水合物；锡化合物与碳化钛量子点的质量比为30～50∶12，优选35～45∶12。上述超声制备锡离子修饰的碳化钛量子点时，超声的功率为400～600 W，时间为100～150 min。In the present invention, the tin compound is a water-soluble divalent tin compound, preferably stannous chloride dihydrate; the mass ratio of the tin compound to the titanium carbide quantum dot is 30-50:12, preferably 35-45:12. When the aforementioned ultrasonic preparation of tin ion-modified titanium carbide quantum dots is performed, the ultrasonic power is 400-600 W and the time is 100-150 min.
本发明中二价锡离子参与构建了Z型异质结复合材料，增加了反应物与催化活性位点的接触，进而提高了光催化的催化效率。本发明公开了上述氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片复合材料在去除水体污染物中的应用或者在光催化产氢中的应用。In the present invention, the divalent tin ions participate in the construction of the Z-type heterojunction composite material, which increases the contact between the reactant and the catalytic active site, thereby improving the catalytic efficiency of photocatalysis. The invention discloses the application of the tungsten oxide nanorod/tin ion-modified titanium carbide quantum dot/indium sulfide nanosheet composite material in removing water body pollutants or in photocatalytic hydrogen production.
本发明公开了含污染物水体的处理方法，包括以下步骤，将上述氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片复合材料加入含污染物的水体中，完成含污染物水体处理。优选的，将上述氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片复合材料加入含污染物的水体中，可见光照射下完成含污染物水体的处理。进一步优选的，污染物为重金属或者有机污染物，比如六价铬、双酚A，尤其是，可见光照射下实现水体中剧毒的六价铬离子完全转化为低毒的三价铬离子，使铬重金属离子的毒性大大降低。The invention discloses a treatment method for water containing pollutants, which includes the following steps: adding the above-mentioned tungsten oxide nanorod/titanium carbide quantum dot/indium sulfide nanosheet composite material modified by tin ions into the water containing pollutants to complete the process of Water treatment. Preferably, the above-mentioned tungsten oxide nanorod/tin ion modified titanium carbide quantum dot/indium sulfide nanosheet composite material is added to the water body containing pollutants, and the treatment of the water body containing pollutants is completed under visible light irradiation. Further preferably, the pollutants are heavy metals or organic pollutants, such as hexavalent chromium and bisphenol A. In particular, under the irradiation of visible light, the highly toxic hexavalent chromium ions in the water body are completely converted into low-toxic trivalent chromium ions, so that The toxicity of chromium heavy metal ions is greatly reduced.
本发明公开了一种光催化产氢的方法，包括以下步骤，将上述氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片复合材料、牺牲剂加入水中，完成光催化产氢。优选的，将上述氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片复合材料加入水中，可见光照射下完成光催化产氢。The invention discloses a method for photocatalytic hydrogen production, comprising the following steps of adding the above-mentioned tungsten oxide nanorod/tin ion modified titanium carbide quantum dot/indium sulfide nanosheet composite material and a sacrificial agent into water to complete photocatalytic hydrogen production . Preferably, the above-mentioned tungsten oxide nanorod/tin ion modified titanium carbide quantum dot/indium sulfide nanosheet composite material is added into water, and photocatalytic hydrogen production is completed under visible light irradiation.
本发明中，光催化产氢过程中的牺牲剂为硫化钠、亚硫酸钠、硫酸钠等，优选为硫化钠和亚硫酸钠。In the present invention, the sacrificial agent in the photocatalytic hydrogen production process is sodium sulfide, sodium sulfite, sodium sulfate, etc., preferably sodium sulfide and sodium sulfite.
有益效果Beneficial effect
本发明公开的含锡离子的Z型异质结复合材料，锡离子的引入加速了电子的转移，增强了光催化性能；在可见光区具有较强的光吸收能力，是一种性能优良的可见光催化材料，用于催化去除六价铬重金属离子等污染物以及光催化分解水产氢时仅需可见光源提供光照；作为具体的氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片复合材料光催化分解水产氢实验，随着光照时间的延长，氢气的产量在增加，在可见光照射5 h后，氢气的产量为75 微摩尔/克，相同条件下硫化铟和未经锡离子修饰的量子点的氧化钨纳米棒/碳化钛量子点/硫化铟纳米片复合材料光照5 h后，氢气产量为10.7 微摩尔/克和12.3微摩尔/克。作为具体的氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片复合材料还原六价铬实验，随着光照时间的延长，六价铬的吸光度逐渐减少，说明水体中六价铬的浓度也在随之降低，在可见光照射30 s、60 s、360 s后，氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片Z型异质结所在的水体中六价铬去除率分别达到68 %、77%、100 %。其中氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片Z型异质结对于水体中六价铬的去除速率是未经锡离子修饰的氧化钨纳米棒/碳化钛量子点/硫化铟纳米片复合材料的2.1倍。而且本发明公开的含锡离子修饰的碳化钛量子点的Z型异质结原料廉价易得，制备方法简单，有利于其进一步的推广使用。The Z-type heterojunction composite material containing tin ions disclosed by the present invention, the introduction of tin ions accelerates the transfer of electrons and enhances the photocatalytic performance; it has strong light absorption capacity in the visible light region, and is a visible light with excellent performance Catalytic materials, used to catalyze the removal of pollutants such as hexavalent chromium heavy metal ions and photocatalytic decomposition of water to produce hydrogen; only visible light sources are required to provide light; as specific tungsten oxide nanorods/tin ion-modified titanium carbide quantum dots/indium sulfide nanosheets In the photocatalytic water splitting hydrogen production experiment of composite materials, with the prolongation of the light time, the hydrogen production increased. After 5 h of visible light irradiation, the hydrogen production was 75 micromol/g. Under the same conditions, indium sulfide and non-tin ion modified The quantum dot-based tungsten oxide nanorods/titanium carbide quantum dots/indium sulfide nanosheet composites were illuminated for 5 h, and the hydrogen production was 10.7 micromol/g and 12.3 micromol/g. As a specific experiment on the reduction of hexavalent chromium by tungsten oxide nanorods/tin ion-modified titanium carbide quantum dots/indium sulfide nanosheet composites, the absorbance of hexavalent chromium gradually decreases with the prolongation of the illumination time, indicating that the hexavalent chromium in water The concentration of is also decreasing accordingly. After 30 s, 60 s, and 360 s of visible light irradiation, the hexavalent Chromium removal rate reached 68%, 77%, 100% respectively. Among them, the removal rate of tungsten oxide nanorods/tin ion-modified titanium carbide quantum dots/indium sulfide nanosheet Z-type heterojunction for hexavalent chromium in water is faster than that of the unmodified tungsten oxide nanorods/titanium carbide quantum dots/ 2.1 times that of indium sulfide nanosheet composites. Moreover, the Z-type heterojunction raw material of the tin ion-modified titanium carbide quantum dot disclosed by the invention is cheap and easy to obtain, and the preparation method is simple, which is beneficial to its further popularization and use.
附图说明Description of drawings
图1为锡离子修饰的碳化钛量子点的透射电镜图。Figure 1 is a transmission electron microscope image of tin ion-modified titanium carbide quantum dots.
图2为锡离子修饰的碳化钛量子点和碳化钛量子点的X射线光电子能谱图。Fig. 2 is an X-ray photoelectron energy spectrum diagram of tin ion-modified titanium carbide quantum dots and titanium carbide quantum dots.
图3为氧化钨纳米棒/锡离子修饰的碳化钛量子点/氧化铟纳米片Z型异质结的扫描电镜图。Fig. 3 is a scanning electron microscope image of a Z-type heterojunction of tungsten oxide nanorods/tin ion-modified titanium carbide quantum dots/indium oxide nanosheets.
图4为氧化钨纳米棒/锡离子修饰的碳化钛量子点/氧化铟纳米片Z型异质结、氧化钨纳米棒/碳化钛量子点/氧化铟纳米片Z型异质结、三氧化钨和硫化铟光催化产氢速率图。Figure 4 shows the Z-type heterojunction of tungsten oxide nanorods/titanium carbide quantum dots/indium oxide nanosheets modified by tin ions, the Z-type heterojunction of tungsten oxide nanorods/titanium carbide quantum dots/indium oxide nanosheets, and tungsten trioxide and indium sulfide photocatalytic hydrogen production rate diagram.
图5为氧化钨纳米棒/锡离子修饰的碳化钛量子点/氧化铟纳米片Z型异质结和氧化钨纳米棒/碳化钛量子点/氧化铟纳米片Z型异质结分别对水中六价铬离子的催化还原转化曲线图。Figure 5 shows the effect of tungsten oxide nanorods/titanium carbide quantum dots/indium oxide nanosheets Z-type heterojunction and tungsten oxide nanorods/titanium carbide quantum dots/indium oxide nanosheets Z-type heterojunction in water respectively. The catalytic reduction conversion curve of chromium ion.
本发明的实施方式Embodiments of the present invention
本发明通过结合简单的超声法、水热法和回流法等制备方法构建了一种含锡离子修饰的碳化钛量子点的Z型异质结用于处理水体污染物以及光催化分解水产氢，其中锡离子修饰的碳化钛量子点具有良好的类金属导电性，是一种良好的介质材料。In the present invention, a Z-type heterojunction of titanium carbide quantum dots modified with tin ions is constructed by combining simple ultrasonic method, hydrothermal method, reflux method and other preparation methods for the treatment of water body pollutants and photocatalytic decomposition of water to produce hydrogen. Among them, titanium carbide quantum dots decorated with tin ions have good metal-like conductivity and are good dielectric materials.
本发明氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片Z型异质结复合材料的制备方法为：首先参照已公开专利（CN111974427A）制备碳化钛量子点，表面带有负离子；然后通过超声辅助将锡化合物中电正性的二价锡离子静电吸附作用锚定在表面带有电负性的-OH和-F末端基团的碳化钛量子点的周围，得到锡离子修饰的碳化钛量子点；之后将参照已公开专利（CN111974427A）制备的三氧化钨纳米棒置于所述量子点的水溶液中，搅拌后静置，得到负载锡离子修饰的量子点的氧化钨纳米棒；将铟化合物、硫化合物、所述负载量子点的氧化钨纳米棒进行回流反应，得到氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片Z型异质结复合材料。本发明中锡离子与碳化钛量子点结合后形成的锡离子修饰的碳化钛量子点参与构建的Z型异质结复合材料，较未经锡离子修饰的碳化钛量子点参与构建的异质结复合材料具有更强的光催化性能。The preparation method of the tungsten oxide nanorod/tin ion modified titanium carbide quantum dot/indium sulfide nanosheet Z-type heterojunction composite material of the present invention is as follows: firstly, referring to the published patent (CN111974427A) to prepare titanium carbide quantum dots with negative ions on the surface ; Then, the electrostatic adsorption of electropositive divalent tin ions in the tin compound is anchored around the titanium carbide quantum dots with electronegative -OH and -F end groups on the surface by ultrasonic assistance, to obtain tin ion modification Titanium carbide quantum dots; then place the tungsten trioxide nanorods prepared with reference to the published patent (CN111974427A) in the aqueous solution of the quantum dots, stir and leave to stand to obtain tungsten oxide nanorods loaded with tin ion-modified quantum dots ; The indium compound, the sulfur compound, and the tungsten oxide nanorods loaded with quantum dots are refluxed to obtain tungsten oxide nanorods/tin ion-modified titanium carbide quantum dots/indium sulfide nanosheet Z-type heterojunction composite materials. In the present invention, the Z-shaped heterojunction composite material is constructed by tin ion-modified titanium carbide quantum dots formed after the combination of tin ions and titanium carbide quantum dots. The composite material has stronger photocatalytic performance.
本发明所涉及的原料都是市售常规产品，具体操作方法以及测试方法都是本领域常规方法，如果没有特别指出温度、气体环境，都是在室温、常规环境下进行。The raw materials involved in the present invention are all commercially available conventional products, and the specific operation methods and testing methods are all conventional methods in this field. If temperature and gas environment are not particularly pointed out, they are all carried out at room temperature and conventional environment.
实施例一锡离子修饰的碳化钛量子点的制备：取120 mL参照已公开专利（CN111974427A实施例一）制备的碳化钛量子点水溶液（100 mg/L）置于反应茄形瓶中，再加入40 mg的氯化亚锡二水合物，再使用真空泵抽出茄形瓶中的空气，使茄形瓶内环境为真空，之后用封口条密封茄形瓶，然后在室温条件下600 W超声2 h，得到锡离子修饰的碳化钛量子点溶液，用于实施例二。Example 1 Preparation of titanium carbide quantum dots modified by tin ions: Take 120 mL of titanium carbide quantum dot aqueous solution (100 mg/L) prepared with reference to the published patent (CN111974427A Example 1) and place it in a reaction eggplant-shaped bottle, then add 40 mg of stannous chloride dihydrate, and then use a vacuum pump to extract the air in the eggplant-shaped bottle to make the environment in the eggplant-shaped bottle a vacuum, then seal the eggplant-shaped bottle with a sealing strip, and then ultrasonicate at 600 W for 2 h at room temperature , to obtain a tin ion-modified titanium carbide quantum dot solution, which is used in Example 2.
附图1为上述的得到的碳化钛量子点的透射电镜图，从上述图中可以明显看到，锡离子修饰的碳化钛量子点尺寸单一且分散均匀。附图2为上述得到的锡离子修饰的碳化钛量子点的X射线光电子能谱图，从图中可以看出，与未经修饰的量子点相比，修饰后的碳化钛量子点有明显锡离子的峰出现，证明了锡离子成功地修饰在碳化钛量子点周围。Accompanying drawing 1 is the TEM image of the titanium carbide quantum dot obtained above, it can be clearly seen from the above figure that the titanium carbide quantum dot modified by tin ions has a single size and is uniformly dispersed. Accompanying drawing 2 is the X-ray photoelectron energy spectrogram of the titanium carbide quantum dot modified by tin ions obtained above, as can be seen from the figure, compared with the unmodified quantum dot, the modified titanium carbide quantum dot has obvious tin The peaks of the ions appear, proving that the tin ions are successfully decorated around the titanium carbide quantum dots.
实施例二 氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片Z型异质结复合材料的制备。Example Preparation of tungsten dioxide nanorod/tin ion modified titanium carbide quantum dot/indium sulfide nanosheet Z-type heterojunction composite material.
具体步骤如下：取0.1 g参照已公开专利（CN111974427A实施例二）制备的三氧化钨纳米棒粉末加入到上述实施例一的锡离子修饰的碳化钛量子点水溶液中，在真空环境下搅拌（1000 rpm）12 h后在室温下静置12 h，然后将其在冻干机中冻干得到负载锡离子修饰的碳化钛量子点的三氧化钨纳米棒粉末。The specific steps are as follows: take 0.1 g of tungsten trioxide nanorod powder prepared with reference to the published patent (CN111974427A embodiment two) and add it to the titanium carbide quantum dot aqueous solution modified by tin ions in the above embodiment one, and stir in a vacuum environment (1000 rpm) for 12 h at room temperature for 12 h, and then freeze-dried in a lyophilizer to obtain tungsten trioxide nanorod powders loaded with tin ion-modified titanium carbide quantum dots.
将57.95 mg负载锡离子修饰的碳化钛量子点的三氧化钨纳米棒粉末分散到10 mL乙二醇；取205 mg三氯化铟四水合物溶于15 mL乙二醇中；再将两种乙二醇溶液在烧瓶中混合，之后加入硫代乙酰胺79 mg；然后将烧瓶接上球形冷凝管和三通阀，接口处密封好，先用真空泵抽走烧瓶和冷凝管中的空气，再用气囊鼓入氩气，将上述装置置于油浴锅中，接入冷凝水后在95 ℃下回流90 min，回流结束后将烧瓶放入冰水混合物中快速降温，冷却后的反应产物先用乙醇和水的混合溶剂洗涤2次，再用乙醇洗涤离心1次，然后在真空干燥箱内干燥至恒重，得到氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片Z型异质结复合材料，用于以下双酚A、六价铬去除以及光催化分解水产氢的处理。Disperse 57.95 mg of tungsten trioxide nanorod powder loaded with tin ion-modified titanium carbide quantum dots into 10 mL of ethylene glycol; take 205 mg of indium trichloride tetrahydrate and dissolve it in 15 mL of ethylene glycol; The ethylene glycol solution was mixed in the flask, and then 79 mg of thioacetamide was added; then the flask was connected to a spherical condenser and a three-way valve, and the interface was sealed, and the air in the flask and the condenser was first evacuated with a vacuum pump, and then Infuse argon gas with an air bag, place the above device in an oil bath, and reflux at 95 °C for 90 min after being connected to condensed water. Wash twice with a mixed solvent of ethanol and water, then wash and centrifuge once with ethanol, and then dry to constant weight in a vacuum oven to obtain tungsten oxide nanorods/tin ion-modified titanium carbide quantum dots/indium sulfide nanosheets Z Type heterojunction composite materials for the following bisphenol A, hexavalent chromium removal and photocatalytic water decomposition for hydrogen production.
附图3为上述氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片Z型异质结的扫描电镜图，从图中可以看出硫化铟纳米片被成功负载。Accompanying drawing 3 is the scanning electron micrograph of the above-mentioned tungsten oxide nanorod/tin ion modified titanium carbide quantum dot/indium sulfide nanosheet Z-type heterojunction. It can be seen from the figure that the indium sulfide nanosheet is successfully loaded.
对比例一 硫化铟纳米片的制备。Comparative Example 1 Preparation of indium sulfide nanosheets.
具体步骤如下：参照已公开专利（CN111974427A对比例二）制备硫化铟纳米片。The specific steps are as follows: refer to the published patent (CN111974427A Comparative Example 2) to prepare indium sulfide nanosheets.
对比例二 氧化钨纳米棒/碳化钛量子点/硫化铟纳米片复合材料的制备。Comparative example Preparation of tungsten dioxide nanorods/titanium carbide quantum dots/indium sulfide nanosheet composites.
具体步骤如下：参照已公开专利（CN111974427A实施例三）制备氧化钨纳米棒/碳化钛量子点/硫化铟纳米片Z型异质结复合材料。The specific steps are as follows: refer to the published patent (CN111974427A Example 3) to prepare a Z-type heterojunction composite material of tungsten oxide nanorod/titanium carbide quantum dot/indium sulfide nanosheet.
实施例三 氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片Z型异质结光催化产氢实验。Example Tungsten trioxide nanorod/tin ion modified titanium carbide quantum dot/indium sulfide nanosheet Z-type heterojunction photocatalytic hydrogen production experiment.
具体步骤如下：取10 mg上述所得的氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片Z型异质复合材料，置于10 mL含0.1 mol/L的硫化钠和0.1 mol/L的亚硫酸钠水溶液中。使用300 W氙灯作为光源，密闭光催化反应器作为反应容器，用注射器每1 h抽取5 mL光催化反应器中的气体。将5 mL气体组分间歇性地提取并注入带有热导检测器的气相色谱仪中。使用氢气摩尔数与峰面积的校准曲线计算产生的氢气量。The specific steps are as follows: Take 10 mg of the above obtained tungsten oxide nanorods/tin ion-modified titanium carbide quantum dots/indium sulfide nanosheet Z-type heterocomposite material, put it in 10 mL containing 0.1 mol/L sodium sulfide and 0.1 mol /L of sodium sulfite aqueous solution. A 300 W xenon lamp was used as the light source, and a closed photocatalytic reactor was used as the reaction vessel, and 5 mL of gas in the photocatalytic reactor was extracted every 1 h with a syringe. 5 mL of gas components were intermittently extracted and injected into a gas chromatograph with a thermal conductivity detector. The amount of hydrogen produced was calculated using a calibration curve of hydrogen moles versus peak area.
附图4为氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片Z型异质结光催化产氢图。从图中可以清楚地看出随着光照时间的延长，氢气的产量在增加。在可见光照射5 h后，氢气的产量为75 微摩尔/克，相同条件下硫化铟（对比例一）和未经锡离子修饰的量子点的氧化钨纳米棒/碳化钛量子点/硫化铟纳米片复合材料（对比例二）光照5 h后，氢气产量分别为10.7 微摩尔/克和12.3微摩尔/克；三氧化钨（CN111974427A实施例二）光照条件下未产生氢气。单纯的碳化钛量子点没有催化作用，不可以光催化产氢。Accompanying drawing 4 is the photocatalytic hydrogen production diagram of Z-type heterojunction of tungsten oxide nanorod/tin ion modified titanium carbide quantum dot/indium sulfide nanosheet. It can be clearly seen from the figure that with the prolongation of the light time, the production of hydrogen gas is increasing. After 5 h of visible light irradiation, the production of hydrogen gas was 75 micromol/g. Under the same conditions, indium sulfide (comparative example 1) and tungsten oxide nanorods/titanium carbide quantum dots/indium sulfide nanorods without tin ion-modified quantum dots After the sheet composite material (Comparative Example 2) was illuminated for 5 hours, the hydrogen production was 10.7 micromol/g and 12.3 micromol/g respectively; tungsten trioxide (CN111974427A Example 2) did not produce hydrogen under light conditions. Pure titanium carbide quantum dots have no catalytic effect and cannot photocatalyze hydrogen production.
实施例四 氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片Z型异质结对水体中六价铬的光催化还原实验。Example 4 The photocatalytic reduction experiment of tungsten oxide nanorods/titanium carbide quantum dots/indium sulfide nanosheets Z-type heterojunction pair in water.
具体步骤如下：取5 mg上述所得的氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片Z型异质复合材料，置于含20 mL浓度为10 mg/L的重铬酸钾水溶液（六价铬离子浓度为20 mg/L）中。黑暗条件下吸附60 min以达到吸附平衡。平衡后使用300 W氙灯作为光源，每3 min取1 mL，用0.22 µm水系滤头过滤后，加入到离心管中，加入显色剂，使用紫外分光光度计检测，由吸光度计算得到六价铬降解效率，其中把六价铬初始浓度标记为100 %。随着光照时间的增加，六价铬浓度逐渐降低伴随着吸光度的逐渐下降，从而得到具体的六价铬催化还原转化曲线。The specific steps are as follows: take 5 mg of the tungsten oxide nanorods/tin ion-modified titanium carbide quantum dots/indium sulfide nanosheet Z-type heterogeneous composite material obtained above, and place it in 20 mL of dichromic acid with a concentration of 10 mg/L. Potassium aqueous solution (hexavalent chromium ion concentration is 20 mg/L). Adsorption was carried out for 60 min in the dark to reach adsorption equilibrium. After equilibrium, use a 300 W xenon lamp as the light source, take 1 mL every 3 min, filter it with a 0.22 µm water filter head, add it to a centrifuge tube, add a chromogenic agent, use a UV spectrophotometer to detect, and calculate hexavalent chromium by absorbance Degradation efficiency, where the initial concentration of hexavalent chromium is marked as 100 %. With the increase of illumination time, the concentration of hexavalent chromium gradually decreased along with the gradual decrease of absorbance, so as to obtain the specific conversion curve of hexavalent chromium catalytic reduction.
附图5为氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片Z型异质结和氧化钨纳米棒/碳化钛量子点/硫化铟纳米片Z型异质结分别对水中六价铬离子的催化还原转化曲线，前60 min为黑暗条件下的吸附平衡时间。从图中可以清楚地看出，随着光照时间的延长，六价铬的吸光度逐渐减少，说明水体中六价铬的浓度也在随之降低，在可见光照射30 s后，氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片Z型异质结所在的水体中六价铬去除率即可达到68 %；在可见光照射60 s时，水体中六价铬去除率提升至77 %；在可见光照射360 s后，催化剂所在的水体中六价铬被完全去除；相同的条件下，三氧化钨粉末（CN111974427A实施例二）光照30 s、60 s、360 s后，水体中的六价铬几乎未被还原去除；硫化铟纳米片（对比例一）光照30 s、60 s、360 s后，水体中的六价铬去除率分别为14 %、15 %、38 %；未经锡离子修饰的氧化钨纳米棒/碳化钛量子点/硫化铟纳米片复合材料（对比例二）光照30 s、60 s、360 s后，水体中的六价铬去除率分别为53%、63 %、86 %。其中氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片Z型异质结对于水体中六价铬的去除速率是未经锡离子修饰的氧化钨纳米棒/碳化钛量子点/硫化铟纳米片复合材料的2.1倍。单纯的碳化钛量子点没有催化作用，不可以催化还原六价铬。Accompanying drawing 5 is that tungsten oxide nanorod/tin ion modified titanium carbide quantum dot/indium sulfide nanosheet Z-type heterojunction and tungsten oxide nanorod/titanium carbide quantum dot/indium sulfide nanosheet Z-type heterojunction respectively react in water The catalytic reduction conversion curve of hexavalent chromium ions, the first 60 min is the adsorption equilibrium time under dark conditions. It can be clearly seen from the figure that the absorbance of hexavalent chromium gradually decreases with the prolongation of the illumination time, indicating that the concentration of hexavalent chromium in the water body also decreases accordingly. After 30 s of visible light irradiation, the tungsten oxide nanorods/ The removal rate of hexavalent chromium in the water body where the titanium carbide quantum dots/indium sulfide nanosheet Z-type heterojunction decorated with tin ions can reach 68%; when the visible light is irradiated for 60 s, the removal rate of hexavalent chromium in the water body increases to 77%. %; after 360 s of visible light irradiation, the hexavalent chromium in the water body where the catalyst is located is completely removed; Hexavalent chromium was hardly removed by reduction; after indium sulfide nanosheets (comparative example 1) were illuminated for 30 s, 60 s, and 360 s, the removal rates of hexavalent chromium in water were 14 %, 15 %, and 38 %; Tungsten oxide nanorods/titanium carbide quantum dots/indium sulfide nanosheets composite material modified by tin ions (comparative example 2) after 30 s, 60 s, and 360 s of light, the removal rates of hexavalent chromium in water were 53%, 63%, respectively. %, 86%. Among them, the removal rate of tungsten oxide nanorods/tin ion-modified titanium carbide quantum dots/indium sulfide nanosheet Z-type heterojunction for hexavalent chromium in water is faster than that of the unmodified tungsten oxide nanorods/titanium carbide quantum dots/ 2.1 times that of indium sulfide nanosheet composites. Pure titanium carbide quantum dots have no catalytic effect and cannot catalyze the reduction of hexavalent chromium.
参照已公开专利（CN111974427A实施例四）的方法进行双酚A降解实验，上述氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片Z型异质复合材料在可见光照射45分钟后，双酚A的去除率达到78%，明显高于无锡离子掺杂复合材料的68%去除率。The degradation experiment of bisphenol A was carried out with reference to the method of the published patent (CN111974427A Example 4). , the removal rate of bisphenol A reached 78%, which was significantly higher than the 68% removal rate of the tin-free ion-doped composite material.
与氧化锡半导体材料与其他半导体结合构成异质结，利用氧化锡这种半导体的特性不同，本发明采用的锡离子是将锡离子与碳化钛量子点结合作为电子传递介质，主体是碳化钛量子点，锡起到促进作用。本发明首先制备碳化钛量子点，之后利用静电吸附作用将电正性的锡离子锚定在表面带-OH和-F末端基团的碳化钛量子点周围，以制备锡离子修饰的碳化钛量子点；然后进一步通过静电吸附自组装作用使锡离子修饰的碳化钛量子点均匀地负载在三氧化钨纳米棒表面，最后通过回流生长硫化铟纳米片构筑氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片Z型异质结复合材料；所得复合材料能够加快光生电子的转移，同时也解决了纳米级量子点易团聚的问题，大大提高了光生电子的利用率。Combining tin oxide semiconductor materials with other semiconductors to form heterojunctions, utilizing the different characteristics of tin oxide semiconductors, the tin ions used in the present invention combine tin ions with titanium carbide quantum dots as an electron transfer medium, and the main body is titanium carbide quantum dots. Point, tin plays a role in promoting. The invention first prepares titanium carbide quantum dots, and then uses electrostatic adsorption to anchor electropositive tin ions around the titanium carbide quantum dots with -OH and -F end groups on the surface to prepare tin ion-modified titanium carbide quantum dots. point; then the TiC quantum dots modified by tin ions are evenly loaded on the surface of tungsten trioxide nanorods through electrostatic adsorption and self-assembly, and finally the tungsten oxide nanorods/titanium carbide modified by tin ions are constructed by reflow growth of indium sulfide nanosheets Quantum dot/indium sulfide nanosheet Z-type heterojunction composite material; the obtained composite material can accelerate the transfer of photogenerated electrons, and at the same time solve the problem that nanoscale quantum dots are easy to agglomerate, greatly improving the utilization rate of photogenerated electrons.

Claims (10)

  1. 一种氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片复合材料，其特征在于，包括氧化钨纳米棒、锡离子修饰的碳化钛量子点以及硫化铟纳米片。A tungsten oxide nanorod/tin ion-modified titanium carbide quantum dot/indium sulfide nanosheet composite material is characterized in that it includes tungsten oxide nanorod, tin ion-modified titanium carbide quantum dot and indium sulfide nanosheet.
  2. 根据权利要求1所述氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片复合材料，其特征在于，在碳化钛量子点上引入锡离子，得到锡离子修饰的碳化钛量子点。Titanium carbide quantum dots/indium sulfide nanosheet composite material modified by tungsten oxide nanorods/tin ions according to claim 1, characterized in that tin ions are introduced into titanium carbide quantum dots to obtain titanium carbide quantum dots modified by tin ions .
  3. 权利要求1所述氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片复合材料的制备方法，其特征在于，包括以下步骤：在碳化钛量子点上引入锡离子，得到锡离子修饰的碳化钛量子点；然后在氧化物纳米棒上负载所述锡离子修饰的碳化钛量子点，得到负载锡离子修饰的碳化钛量子点的氧化钨纳米棒；再将负载锡离子修饰的碳化钛量子点的氧化钨纳米棒、铟化合物和硫化合物在溶剂中反应，得到氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片复合材料。The preparation method of the titanium carbide quantum dot/indium sulfide nanosheet composite material modified by tungsten oxide nanorods/tin ions according to claim 1, characterized in that it comprises the following steps: introducing tin ions on the titanium carbide quantum dots to obtain tin ions Modified titanium carbide quantum dots; then load the tin ion-modified titanium carbide quantum dots on the oxide nanorods to obtain tungsten oxide nanorods loaded with tin ion-modified titanium carbide quantum dots; then load the tin ion-modified carbonized Tungsten oxide nanorods of titanium quantum dots, indium compounds and sulfur compounds react in a solvent to obtain tungsten oxide nanorods/tin ion-modified titanium carbide quantum dots/indium sulfide nanosheet composite materials.
  4. 根据权利要求3所述氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片复合材料的制备方法，其特征在于，铟化合物为四水合三氯化铟或者四点五水合硝酸铟；硫化合物为九水合硫化钠、硫代乙酰胺或者硫脲等硫化合物；溶剂为醇。According to the preparation method of the titanium carbide quantum dot/indium sulfide nanosheet composite material modified by tungsten oxide nanorods/tin ions according to claim 3, it is characterized in that the indium compound is indium trichloride tetrahydrate or indium nitrate tetrahydrate The sulfur compound is sulfur compound such as sodium sulfide nonahydrate, thioacetamide or thiourea; the solvent is alcohol.
  5. 根据权利要求3所述氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片复合材料的制备方法，其特征在于，以锡化合物、碳化钛量子点为原料，采用超声法得到锡离子修饰的碳化钛量子点。According to the preparation method of the titanium carbide quantum dot/indium sulfide nanosheet composite material modified by tungsten oxide nanorods/tin ions according to claim 3, it is characterized in that, using tin compounds and titanium carbide quantum dots as raw materials, the tin is obtained by ultrasonic method Ion-modified titanium carbide quantum dots.
  6. 根据权利要求3所述氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片复合材料的制备方法，其特征在于，锡化合物为氯化亚锡二水合物；氯化亚锡二水合物与碳化钛量子点的质量比为30～50∶12；超声法制备锡离子修饰的碳化钛量子点时，超声的功率为400～600 W，时间为100～150 min。According to the preparation method of the titanium carbide quantum dot/indium sulfide nanosheet composite material of the described tungsten oxide nanorod/tin ion modification of claim 3, it is characterized in that, tin compound is stannous chloride dihydrate; The mass ratio of hydrate to titanium carbide quantum dots is 30-50:12; when tin ion-modified titanium carbide quantum dots are prepared by ultrasonic method, the ultrasonic power is 400-600 W and the time is 100-150 min.
  7. 权利要求1所述氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片复合材料在去除水体污染物中的应用或者在光催化产氢中的应用。The application of the tungsten oxide nanorod/tin ion modified titanium carbide quantum dot/indium sulfide nanosheet composite material in claim 1 in the removal of water pollutants or in the photocatalytic hydrogen production.
  8. 一种含污染物水体的处理方法，其特征在于，包括以下步骤，将权利要求1所述氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片复合材料加入含污染物的水体中，光催化完成含污染物水体处理。A treatment method for water containing pollutants, characterized in that it comprises the steps of adding the titanium carbide quantum dots/indium sulfide nanosheet composite material modified with tungsten oxide nanorods/tin ions according to claim 1 to the water containing pollutants Among them, photocatalysis completes the treatment of water containing pollutants.
  9. 一种光催化产氢的方法，其特征在于，包括以下步骤，将权利要求1所述氧化钨纳米棒/锡离子修饰的碳化钛量子点/硫化铟纳米片复合材料、牺牲剂加入水中，完成光催化产氢。A method for photocatalytic hydrogen production, characterized in that it comprises the steps of adding titanium carbide quantum dots/indium sulfide nanosheet composite materials and sacrificial agents modified by tungsten oxide nanorods/tin ions according to claim 1 into water, and completing Photocatalytic hydrogen production.
  10. 根据权利要求8或者9所述的方法，其特征在于，光催化为可见光催化。The method according to claim 8 or 9, characterized in that the photocatalysis is visible light catalysis.
PCT/CN2021/114162 2021-08-23 2021-08-23 Tungsten oxide nanorod/tin ion modified titanium carbide quantum dot/indium sulfide nanosheet composite material, and preparation method therefor and use thereof WO2023023919A1 (en)

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CN105470486A (en) * 2015-12-25 2016-04-06 陕西科技大学 Preparation method of granular tin dioxide/two-dimensional nano titanium carbide composite material
CN107742702A (en) * 2017-09-21 2018-02-27 天津大学 The CNT and tin ash of three-dimensional " upper thread face " structure are modified titanium carbide lithium ion battery negative material and preparation method
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Publication number Priority date Publication date Assignee Title
CN105470486A (en) * 2015-12-25 2016-04-06 陕西科技大学 Preparation method of granular tin dioxide/two-dimensional nano titanium carbide composite material
CN107742702A (en) * 2017-09-21 2018-02-27 天津大学 The CNT and tin ash of three-dimensional " upper thread face " structure are modified titanium carbide lithium ion battery negative material and preparation method
CN110931741A (en) * 2019-11-26 2020-03-27 上海大学 Tin sulfide quantum dot loaded titanium carbide composite nano material and preparation method thereof
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