WO2011050516A1 - Method of testing titania nanotubes for adsorbing-degrading performances on micro-interface thereof - Google Patents

Method of testing titania nanotubes for adsorbing-degrading performances on micro-interface thereof Download PDF

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WO2011050516A1
WO2011050516A1 PCT/CN2009/074642 CN2009074642W WO2011050516A1 WO 2011050516 A1 WO2011050516 A1 WO 2011050516A1 CN 2009074642 W CN2009074642 W CN 2009074642W WO 2011050516 A1 WO2011050516 A1 WO 2011050516A1
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titanium dioxide
nanotubes
adsorption
simulated
methylene blue
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PCT/CN2009/074642
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French (fr)
Chinese (zh)
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陈军
顾娟红
卢艳光
郑寿荣
唐玉琼
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Chen Jun
Gu Juanhong
Lu Yanguang
Zheng Shourong
Tang Yuqiong
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Priority to PCT/CN2009/074642 priority Critical patent/WO2011050516A1/en
Publication of WO2011050516A1 publication Critical patent/WO2011050516A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/13—Nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • the invention belongs to the technical field of product performance detection, and relates to a method for measuring photocatalytic ability of a micro interface of titanium dioxide nanotubes, and particularly relates to a simulated pollutant methylene blue which can effectively determine the photocatalytic effect of micro interface of titanium dioxide (Ti0 2 ) nanotubes.
  • MB Method of adsorption-degradation performance. Background technique
  • titanium dioxide (Ti0 2 ) nanomaterials As a semiconductor photocatalyst with excellent comprehensive performance, titanium dioxide (Ti0 2 ) nanomaterials have superior characteristics such as volume effect, surface effect, quantum size effect and macroscopic quantum tunneling due to the surface characteristics of their microstructure, especially titanium dioxide (Ti0 2 ).
  • the photocatalytic ability of nano-material micro-interface adsorption-degradation of organic pollutants has shown an attractive prospect in removing refractory pollutants in various environmental media.
  • the use of nanotechnology has low energy consumption, simple operation and mild reaction conditions.
  • the advantages of reducing secondary pollution, etc. can effectively completely inorganicize many toxic organic pollutants in the environment, and thus have attracted widespread attention and become a hot spot for development research.
  • Ti0 2 titanium dioxide
  • Anionic free radicals preferentially degrade the pollutants adsorbed at the micro interface, making them harmless.
  • the photochemical activity of the micro-interface of cerium oxide (Ti0 2 ) nanotubes can also be stimulated by the release of new eco-oxygen [0] due to its lattice defects and through the internal migration of the matrix material in contact with the surface of the nano-titanium dioxide (Ti0 2 ) material.
  • the components react to form active groups such as active hydroxyl radicals and peroxyhydroxy radicals, which weaken the aging resistance of the matrix material and shorten the service life of the material. Therefore, how to integrate the micro-interface effect of nano-titanium dioxide (Ti0 2 ) materials with the improvement of the aging resistance requirements of the matrix materials is a problem that must be perfected when researching and developing application products.
  • the photoactivity of nano-titanium dioxide (Ti0 2 ) can be divided into photocatalytic action at the micro interface and photochemical reaction caused by self-lattice defects. Since the two generate different radicals, the action objects are different, so the effect of these free radicals In the photocatalytic process, free radicals are generated and act on the surface of the material, which has the function of sterilization and decontamination. In the photochemical active reaction process, free radicals are generated and act on the interior of the material, thus degrading the matrix material. , destructive effect.
  • the adsorption-degradation performance of the nano-titanium dioxide ( ⁇ 0 2 ) micro-interface effect is mainly based on the effective utilization of its photocatalysis. In consideration of the action, the efficiency of the photocatalytic reaction was calculated by simulating the adsorption isotherm, photodegradation curve, degradation rate and kinetics of the pollutants, and the adsorption-degradation performance of the material was evaluated.
  • nano-titanium dioxide (Ti0 2 ) has been widely used in plastics and fiber masterbatch, leather, interior and exterior wall coatings, etc., giving the materials antibacterial, anti-mildew, air purification, surface self-cleaning, etc.
  • the invention aims to provide a method for measuring the adsorption-degradation performance of a micro interface of titanium dioxide nanotubes, and solves the method for measuring the adsorption-degradation performance of the micro interface of the titanium dioxide nanotubes in the prior art and products, which results in failure to impart processing and processing energy. Problems such as performance and quality testing of nano-materials with special effects such as antibacterial, anti-mildew, air purification, and surface self-cleaning.
  • a method for determining the adsorption-degradation performance of a micro interface of a titanium dioxide nanotube characterized in that the method comprises the following steps:
  • step (1) of the method is selected from the group consisting of methylene blue.
  • the synthesis of the titanium dioxide nanotubes in the method step (2) comprises the steps of forming a titanium dioxide nanotube precursor and the step of synthesizing the titanium dioxide nanotubes with the titanium dioxide nanotube precursor.
  • the step of forming the titanium dioxide nanotube precursor in the step (2) of the method comprises: using titanium dioxide in the reaction vessel as an reaction medium, treating with a strong alkali, heating and dissolving, and cooling to form a crystal.
  • the synthesis step of the titanium dioxide (Ti0 2 ) nanotube precursor comprises: adding 16 g of NaOH to 40 ml of distilled water, and after completely dissolving, taking Ti0 2 2 g, stirring at room temperature for 2 h, placed in an oven at 150 ° C, and heating for 5 hours, and taking out. After cooling, the resulting cake was chopped. Continue to heat in an oven at 150 °C for 10 h. The mixture was taken out and cooled, stirred well, and placed in a reaction vessel, and heated at 150 ° C for two days. After cooling, the lower part of the kettle is a relatively loose paste, and the supernatant is decanted to obtain dioxane. Titanium ( ⁇ 0 2 ) nanotube precursor.
  • the step of synthesizing the titanium dioxide nanotubes in the titanium dioxide nanotube precursor in the method step (2) comprises pickling the titanium dioxide nanotube precursor to a pH of 6 to 6.5 and baking at different temperatures to form titanium dioxide having different properties.
  • the steps of the nanotubes comprises pickling the titanium dioxide nanotube precursor to a pH of 6 to 6.5 and baking at different temperatures to form titanium dioxide having different properties.
  • the titanium dioxide (Ti0 2 ) nanotube is synthesized by placing a titanium dioxide (Ti0 2 ) nanotube precursor in a large beaker, adjusting the pH to 2.5, stirring, acid exchange for 2 h, washing to pH 6 to 6.5, 60 ° C. Dry in an oven. Titanium dioxide (Ti0 2 ) nanotubes dried at 60 degrees were calcined at different temperatures to obtain different types of titanium dioxide (Ti0 2 ) nanotubes. The firing conditions were as follows: The heating rate was 1 degree/minute, and calcined at 200 to 600 degrees for 5 hours.
  • the method for characterizing the synthesized titanium dioxide nanotubes in the method step (2) comprises characterizing the titanium dioxide nanotubes by transmission electron microscopy, BET specific surface area, and X-ray diffraction.
  • the TiO 2 nanotubes having photocatalytic activity are characterized by a transmission electron microscope method, and the tube diameter is about 3 nm, and the tube wall is 3 to 4 layers.
  • the X-ray diffraction method is used to characterize the photocatalytic activity of the titanium dioxide nanotubes, and the nanotubes having a calcination temperature lower than 400 ° C are titanate type, and the nanotubes above 400 ⁇ are burned. Titanium dioxide anatase type.
  • the adsorption and photodegradation rate of the simulated pollutants by the titanium dioxide nanotubes under different conditions are determined, and the adsorption and photodegradation rates of the simulated contaminant methylene blue by the obtained titanium dioxide nanotubes at different calcination temperatures are determined.
  • the adsorption-degradation performance of the different types of titanium dioxide (T) 2 nanotubes on the simulated pollutant methylene blue (MB) was evaluated by studying adsorption isotherms, photodegradation curves, degradation rates and kinetic studies. of.
  • the adsorption isotherm of methylene blue (MB) on titanium dioxide (Ti0 2 ) nanotubes accords with the Langmuir adsorption model.
  • the titanium dioxide (Ti0 2 ) nanotubes obtained at the calcination temperature of 400 ⁇ have the best adsorption-degradation effect on the simulated pollutant methylene blue (MB), and the degradation rate can reach 85%.
  • the kinetic study of the present invention reflects that the photodegradation of the simulated pollutant methylene blue (MB) by titanium dioxide (Ti0 2 ) nanotubes is a comprehensive process, and is affected by both adsorption and surface photolysis processes.
  • the cerium oxide (Ti0 2 ) nanotubes first adsorb the simulated contaminant methylene blue (MB) and then degrade on the surface.
  • the advantage of the present invention over the prior art solutions is - 1.
  • the technical scheme of the present invention is characterized by transmission electron microscopy (TEM), BET specific surface area, X-ray diffraction (XRD), and adsorption isotherm of simulated pollutant methylene blue (MB) by studying different types of titanium dioxide (Ti02) nanotubes. Wire, photodegradation curve, degradation rate and kinetics study provide an effective method for evaluating the adsorption-degradation performance of titanium dioxide (Ti0 2 ) nanotubes, which is the decontamination ability of cerium oxide ( ⁇ 0 2 ) nanotube products.
  • Technical support is provided for the standardization of evaluation methods.
  • a measuring method of the present invention can be best adsorbed titanium oxide (Ti0 and 2) nanotubes - degradation by adsorption - the optimum conditions can be obtained titanium oxide (Ti0 and 2) optimization of nanotubes of degradation.
  • the titanium dioxide nanotubes synthesized by the method of the invention have good adsorption effect on methylene blue, and can effectively inhibit the migration of dyes; the nanotubes have good photodegradation effect on methylene blue under the experimental conditions. In the actual fabric and environmental water, the nanotubes will effectively degrade various pollutants and achieve purification.
  • the present invention provides a method for evaluating the micro-interface properties of nano-titanium dioxide (Ti0 2 ) based on the exploration product, and the nanotube precursor is prepared by using titanium dioxide (Ti0 2 ), pickling and drying at different temperatures.
  • the sub-step calcination was carried out to obtain different titania (Ti0 2 ) nanotubes, which were characterized by transmission electron microscopy (TEM), BET specific surface area, X-ray diffraction (XRD), and methylene blue by titanium dioxide (Ti0 2 ) nanotubes.
  • TEM transmission electron microscopy
  • XRD X-ray diffraction
  • MB Adsorption-degradation performance evaluation, providing technical support for the standardization of evaluation methods.
  • FIG. 1 is a transmission electron microscope (TEM) FIG titania (Ti0 and 2) nanotubes pickling and drying 60 ° C;
  • FIG. 2 is a transmission titania (Ti0 and 2) pickling nanotubes drying 60 ° C 300 ° C calcination Electron microscopy (TEM) image;
  • Figure 3 is a transmission electron microscope (TEM) image of titanium dioxide (Ti0 2 ) nanotubes after baking at 500 ° C for 500 C baking;
  • TEM transmission electron microscope
  • FIG. 4 is calcined at different temperatures titania X-ray diffraction (Ti0 2) nanotubes (XRD) pattern;
  • FIG. 5 is a different firing temperature of titanium dioxide (Ti0 2) nanotubes to blue light degradation methylene curve;
  • FIG. 6 is a different firing temperature of titanium dioxide (Ti0 2 ) the degradation rate of nanotubes to the simulated pollutant methylene blue (MB);
  • Figure 7 shows the simulated contaminant methylene blue (MB) in titanium dioxide (Ti0 2 ) at different calcination temperatures. Adsorption isotherms on nanotubes. detailed description
  • Philips Tecnai-12 transmission electron microscope HRTEM
  • D/max-RA type X-ray diffractometer RigaKu TM , JP
  • Cary 5000 UV-VIS spectrophotometer Varian TM , USA
  • sodium hydroxide NaOH
  • AR titanium dioxide
  • X-ray diffraction (XRD) measurement conditions Starting angle: 5; End angle: 70; Step size: 0.02; Scanning speed: 10; Integration time: 0.1; Target type: Cu; Tube pressure: 50 Kvl 50 mA; 1, 1, 0.6, 0.6; Filter: Graphite.
  • Ti0 2 Titanium Dioxide
  • Ti0 2 Tin Dioxide
  • 16 g of NaOH was added to 40 ml of distilled water. After completely dissolving, Ti0 2 2 g was taken , stirred at room temperature for 2 h, placed in an oven at 150 ° C, and heated for 5 h before being taken out. After cooling, the resulting cake was chopped. Continue to heat in an oven at 150 °C for 10 h. Take out the cooling, stir and hook, continue to put in the reaction kettle, and heat at 150 °C for two days. After cooling, the lower part of the kettle was a relatively loose paste, and the supernatant was decanted to obtain a titanium dioxide (Ti0 2 ) nanotube precursor.
  • Ti0 2 titanium dioxide nanotubes
  • Ti0 2 titanium dioxide nanotubes
  • pH was adjusted to 2.5, with stirring, nucleotide exchange 2H; until the pH was 6 ⁇ 6.5, 60 ⁇ drying oven.
  • the 60-degree dried nanotubes are calcined at different temperatures to obtain catalysts of different properties.
  • the baking conditions were as follows: the heating rate was 1 degree/minute, and the firing was performed at 200 to 600 degrees for 5 hours.
  • Table 1 BET specific surface area calcination temperature of titanium dioxide (Ti0 2 ) nanotubes at different calcination temperatures / ° c Unbaked 200 300 350 400 500 600 700 specific surface area / m 2 * gl 263.5 250.0 256.1 284.9 193.8 83.8 53.5 22.6
  • the data in the table shows The relationship between the BET specific surface area of the titanium dioxide (Ti0 2 ) nanotubes and the calcination temperature is basically that the specific surface area decreases as the calcination temperature increases, which is more remarkable in the high temperature region.
  • the raw material titanium dioxide is processed to form a nanotube, and its BET specific surface area is relatively increased (the Ti0 2 specific surface area of the raw material is less than 10 m 2 , gl ). The increase in specific surface area will be more effective for the adsorption of dye molecules.
  • Figure 2 shows, the firing temperature is lower than 400 ⁇ titanium oxide (Ti0 and 2) titanate nanotubes type, above 400 ° C titanium dioxide (Ti0 and 2) nanotube anatase, 400 ° C is titanium dioxide (Ti0 and 2 ) The crystallographic point of the nanotube.
  • the adsorption isotherm of titanium dioxide (Ti0 2 ) nanotubes on the simulated pollutant methylene blue (MB) can be seen from Figure 7.
  • the adsorption isotherm of the simulated pollutant methylene blue (MB) on the titanium dioxide ( ⁇ 0 2 ) nanotubes is consistent with Langmuir.
  • the adsorption model that is, the adsorption of the simulated pollutant methylene blue (MB) by titanium dioxide (Ti0 2 ) nanotubes reaches saturation at a low concentration, and then the saturated adsorption amount of methylene blue (MB) is basically unchanged as the equilibrium concentration increases.
  • the 300 'C calcined titanium dioxide (Ti0 2 ) nanotubes had a saturated adsorption capacity for methylene blue (MB) of 130 mg/g.
  • Ti0 2 methylene blue other firing temperature
  • Ti0 2 nanotubes of titanium dioxide (MB) adsorption amount table BET specific surface area data has a good correlation, i.e., titanium dioxide ( ⁇ 0 2)
  • ⁇ 0 2 titanium dioxide
  • titanium dioxide (Ti0 2 ) nanotubes as a simulated pollutant methylene blue (MB) is a comprehensive process, which is affected by both adsorption and surface photolysis.
  • the titanium dioxide (Ti0 2 ) nanotubes first adsorbed the surface of the simulated pollutant methylene blue (MB) and degraded on the surface.
  • the tube is anatase crystal form, and the degradation of contaminants by anatase is more effective than other crystal forms.
  • Table 2 also reflects that the higher the proportion of titanium dioxide (1 0 2 ) nanotube anatase crystal form, the simulated pollutants The photodegradation rate constant of methylene blue (MB) is larger.
  • the comprehensive evaluation showed that the adsorption-degradation evaluation of the micro-interface effect of titanium dioxide (Ti0 2 ) nanotubes using methylene blue (MB) as a simulated pollutant was effective, and anatase-type nanotube titanium dioxide (Ti0 2 ) nanotube pairs were also found.
  • the simulated pollutant methylene blue (MB) has the best degradation efficiency, up to 85%.
  • the adsorption-degradation of the widely used titanium dioxide (Ti0 2 ) nanomaterials by using methylene blue (MB) as a simulated pollutant is studied, and the nanotube precursor is prepared by titanium dioxide ( ⁇ 0 2 ), pickled and baked. After drying, the calcination was carried out at different temperatures to obtain different titania (Ti0 2 ) nanotubes, which were characterized by transmission electron microscopy (TEM), BET specific surface area and X-ray diffraction (XRD), and passed through titanium dioxide (Ti0 2 ).
  • TEM transmission electron microscopy
  • XRD X-ray diffraction
  • the adsorption isotherms, photodegradation curves, degradation rates and kinetics of the simulated pollutant methylene blue (MB) were calculated by nanotubes.
  • the degradation rate of the photocatalytic reaction of the dye methylene blue (MB) was calculated to evaluate the adsorption and photodegradation of the material. performance.
  • the titanium dioxide (Ti0 2 ) nanotubes used in the experiment have a good adsorption effect on the simulated pollutant methylene blue (MB), and the highest adsorption capacity can reach 130 mg/g.
  • the titanium dioxide (Ti0 2 ) nanotubes under the experimental conditions simulate the pollutant methylene blue ( MB) has good photodegradation and the highest degradation rate is 85%.
  • Studies have shown that the adsorption-degradation performance evaluation of the micro-interface effect of titanium dioxide (Ti0 2 ) nanomaterials on the simulated pollutant methylene blue (MB) can be applied to the production process to impart antibacterial, anti-mildew, air purification and surface self-cleaning.
  • the evaluation of the performance and quality of nano-materials with special effects is conducive to providing corresponding technical support for further improving the standards of nano-product technology.

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Abstract

A method of testing titania nanotubes for adsorbing-degrading performances on micro-interface thereof is characterized in that the method includes the following steps; (1) choosing a proper simulated contaminant, (2) synthesizing titania nanotubes and characterizing the same, (3) testing the titania nanotubes for adsorbing and photodegrading ratios of the simulated contaminant under different conditions. Testing titania nanotubes for methylene blue adsorbing and degrading performances can provide a mean for evaluating the qualities of nano-materials capable of imparting to products special functions, such as bacteria repellence, mildew proof, air purification, and surface self-cleaning.

Description

二氧化钛纳米管微界面的吸附 -降解性能测定方法 技术领域  Adsorption-degradation performance determination method of titanium dioxide nanotube micro interface
本发明属于产品性能检测技术领域，涉及一种二氧化钛纳米管微界面的 光催化能力测定方法， 具体涉及了一种可有效测定二氧化钛 (Ti02)纳米管微 界面光催化效应的模拟污染物一亚甲基蓝 (MB) 吸附 -降解性能的方法。 背景技术 The invention belongs to the technical field of product performance detection, and relates to a method for measuring photocatalytic ability of a micro interface of titanium dioxide nanotubes, and particularly relates to a simulated pollutant methylene blue which can effectively determine the photocatalytic effect of micro interface of titanium dioxide (Ti0 2 ) nanotubes. (MB) Method of adsorption-degradation performance. Background technique
作为一种综合性能优良的半导体光催化剂， 二氧化钛 (Ti02)纳米材料因 其微观结构的表面特征具有体积效应、 表面效应、 量子尺寸效应和宏观量子 隧道效应等优越特性， 尤其是二氧化钛 (Ti02) 纳米材料微界面的吸附 -降解 有机污染物的光催化能力在去除各种环境介质中难降解的污染物方面展现 出诱人的前景， 利用纳米技术具有能耗低、 操作简单、 反应条件温和、 减少 二次污染等优点， 能有效地将有环境中许多有毒有机污染物完全无机化， 因 而已引起人们的广泛关注， 成为开发研究的热点。 As a semiconductor photocatalyst with excellent comprehensive performance, titanium dioxide (Ti0 2 ) nanomaterials have superior characteristics such as volume effect, surface effect, quantum size effect and macroscopic quantum tunneling due to the surface characteristics of their microstructure, especially titanium dioxide (Ti0 2 ). The photocatalytic ability of nano-material micro-interface adsorption-degradation of organic pollutants has shown an attractive prospect in removing refractory pollutants in various environmental media. The use of nanotechnology has low energy consumption, simple operation and mild reaction conditions. The advantages of reducing secondary pollution, etc., can effectively completely inorganicize many toxic organic pollutants in the environment, and thus have attracted widespread attention and become a hot spot for development research.
二氧化钛 (Ti02)纳米材料微界面的吸附-降解作用是通过光生载流子迁 移到纳米管微界面， 与表面的吸附水和氧气充分接触， 产生活性氢氧自由基 ( · OH ) 和超氧阴离子自由基， 优先降解吸附在微界面的污染物， 使之成 为无害物质。 当然， 二氧化钕 (Ti02)纳米管微界面的光化学活性还可因其晶 格缺陷受激释放新生态氧 [0] 并通过物质迁移与纳米二氧化钛 (Ti02) 材料 表面接触的基体物质内部组分反应生成活性氢氧自由基、过氧羟基游离基等 氧化基团， 削弱基体材料的耐老化性能， 缩短材料的使用寿命。 因此， 如何 将纳米二氧化钛（Ti02)材料的微界面效应同改善基体材料的耐老化性要求有 机地统一起来， 是研究开发应用产品时必须完善的问题。 The adsorption-degradation of the micro-interface of titanium dioxide (Ti0 2 ) nanomaterials is caused by the migration of photogenerated carriers to the micro-interface of the nanotubes, which is in full contact with the adsorbed water and oxygen on the surface to produce active hydroxyl radicals ( · OH ) and superoxide. Anionic free radicals preferentially degrade the pollutants adsorbed at the micro interface, making them harmless. Of course, the photochemical activity of the micro-interface of cerium oxide (Ti0 2 ) nanotubes can also be stimulated by the release of new eco-oxygen [0] due to its lattice defects and through the internal migration of the matrix material in contact with the surface of the nano-titanium dioxide (Ti0 2 ) material. The components react to form active groups such as active hydroxyl radicals and peroxyhydroxy radicals, which weaken the aging resistance of the matrix material and shorten the service life of the material. Therefore, how to integrate the micro-interface effect of nano-titanium dioxide (Ti0 2 ) materials with the improvement of the aging resistance requirements of the matrix materials is a problem that must be perfected when researching and developing application products.
纳米二氧化钛 (Ti02)的光活性实际可分为微界面的光催化作用和自身 晶格缺陷引起的光化学反应， 由于两者产生自由基的场合不同， 作用对象不 同， 所以这些自由基的作用效果也就不同： 在光催化过程中， 自由基产生并 作用于材料表面， 具有杀菌、 去污的功能； 而在光化学活性反应过程中， 自 由基产生并作用于材料内部， 因而对基体材料起降解、 破坏作用。 确定纳米 二氧化钛 (Τί02)微界面效应的吸附 -降解性能主要是基于有效利用其光催化 作用的考虑， 通过模拟污染物的吸附等温线、 光降解曲线、 降解率及动力学 研究， 计算光催化反应的效率并以此来评价该材料的吸附 -降解性能。 The photoactivity of nano-titanium dioxide (Ti0 2 ) can be divided into photocatalytic action at the micro interface and photochemical reaction caused by self-lattice defects. Since the two generate different radicals, the action objects are different, so the effect of these free radicals In the photocatalytic process, free radicals are generated and act on the surface of the material, which has the function of sterilization and decontamination. In the photochemical active reaction process, free radicals are generated and act on the interior of the material, thus degrading the matrix material. , destructive effect. The adsorption-degradation performance of the nano-titanium dioxide (Τί0 2 ) micro-interface effect is mainly based on the effective utilization of its photocatalysis. In consideration of the action, the efficiency of the photocatalytic reaction was calculated by simulating the adsorption isotherm, photodegradation curve, degradation rate and kinetics of the pollutants, and the adsorption-degradation performance of the material was evaluated.
经文献检索，纳米二氧化钛 (Ti02)已广泛应用于塑料及纤维母粒、皮革、 内外墙涂料等材料中， 赋予了材料抗菌、 防霉、 净化空气、 表面自清洁等功 能， 但目前尚无有关其微界面吸附-降解性能评测方面的研究， 因此， 对直 接复合到基体材料的纳米二氧化钛 (Ti02)的微界面效应评价十分必要。 发明内容 Through literature search, nano-titanium dioxide (Ti0 2 ) has been widely used in plastics and fiber masterbatch, leather, interior and exterior wall coatings, etc., giving the materials antibacterial, anti-mildew, air purification, surface self-cleaning, etc. Regarding the evaluation of its micro-interface adsorption-degradation performance, it is necessary to evaluate the micro-interface effect of nano-titanium dioxide (Ti0 2 ) directly bonded to the matrix material. Summary of the invention
本发明目的在于提供一种二氧化钛纳米管微界面的吸附-降解性能测定 方法， 解决了现有技术和产品中缺乏二氧化钛纳米管微界面的吸附-降解性 能的测定方法， 导致无法对生产加工能赋予产品抗菌、 防霉、 净化空气、 表 面自清洁等特殊功效的纳米材料性能品质测试等问题。  The invention aims to provide a method for measuring the adsorption-degradation performance of a micro interface of titanium dioxide nanotubes, and solves the method for measuring the adsorption-degradation performance of the micro interface of the titanium dioxide nanotubes in the prior art and products, which results in failure to impart processing and processing energy. Problems such as performance and quality testing of nano-materials with special effects such as antibacterial, anti-mildew, air purification, and surface self-cleaning.
为了解决现有技术中的这些问题， 本发明提供的技术方案是：  In order to solve the problems in the prior art, the technical solution provided by the present invention is:
一种二氧化钛纳米管微界面的吸附-降解性能测定方法， 其特征在于所 述方法包括以下步骤：  A method for determining the adsorption-degradation performance of a micro interface of a titanium dioxide nanotube, characterized in that the method comprises the following steps:
( 1 ) 遴选合适的模拟污染物；  (1) selecting suitable simulated pollutants;
( 2 ) 合成二氧化钛纳米管以及对合成的二氧化钛纳米管进行表征； (2) synthesizing titanium dioxide nanotubes and characterizing the synthesized titanium dioxide nanotubes;
( 3 )测定不同条件下二氧化钛纳米管对模拟污染物的吸附、 光降解率。 优选的， 所述方法步骤 （1 ) 中模拟污染物选自亚甲基蓝。 (3) Determination of adsorption and photodegradation rate of simulated pollutants by titanium dioxide nanotubes under different conditions. Preferably, the simulated pollutant in step (1) of the method is selected from the group consisting of methylene blue.
优选的， 所述方法步骤 （2 ) 中二氧化钛纳米管的合成包括形成二氧化 钛纳米管前驱体的步骤和二氧化钛纳米管前驱体合成二氧化钛纳米管的步 骤。  Preferably, the synthesis of the titanium dioxide nanotubes in the method step (2) comprises the steps of forming a titanium dioxide nanotube precursor and the step of synthesizing the titanium dioxide nanotubes with the titanium dioxide nanotube precursor.
优选的， 所述方法步骤 （2 ) 中二氧化钛纳米管前驱体的形成步骤包括 二氧化钛在反应釜内以水溶液为反应介质， 经强碱处理， 加热溶解， 冷却结 晶形成。  Preferably, the step of forming the titanium dioxide nanotube precursor in the step (2) of the method comprises: using titanium dioxide in the reaction vessel as an reaction medium, treating with a strong alkali, heating and dissolving, and cooling to form a crystal.
更优选的， 二氧化钛 (Ti02)纳米管前驱体的合成步骤包括- 取 16gNaOH加入 40ml蒸馏水， 完全溶解后， 取 Ti02 2g , 室温下搅拌 2h， 放入烘箱 150 °C , 加热 5h后取出。 冷却， 将得到的块状物捣碎。 继续放 入烘箱中 150 °C加热 10h。取出冷却，搅拌均匀，继续放入反应釜中， 150 °C 加热两天。 冷却后， 釜中下部为比较松散的糊状物， 倒掉上清液， 得到二氧 化钛 (Τί02)纳米管前驱体。 More preferably, the synthesis step of the titanium dioxide (Ti0 2 ) nanotube precursor comprises: adding 16 g of NaOH to 40 ml of distilled water, and after completely dissolving, taking Ti0 2 2 g, stirring at room temperature for 2 h, placed in an oven at 150 ° C, and heating for 5 hours, and taking out. After cooling, the resulting cake was chopped. Continue to heat in an oven at 150 °C for 10 h. The mixture was taken out and cooled, stirred well, and placed in a reaction vessel, and heated at 150 ° C for two days. After cooling, the lower part of the kettle is a relatively loose paste, and the supernatant is decanted to obtain dioxane. Titanium (Τί0 2 ) nanotube precursor.
优选的， 所述方法步骤 （2 ) 中二氧化钛纳米管前驱体合成二氧化钛纳 米管的步骤包括将二氧化钛纳米管前驱体酸洗至 ρΗ为 6〜6.5烘干在不同温 度条件下焙烧形成不同性质的二氧化钛纳米管的步骤。  Preferably, the step of synthesizing the titanium dioxide nanotubes in the titanium dioxide nanotube precursor in the method step (2) comprises pickling the titanium dioxide nanotube precursor to a pH of 6 to 6.5 and baking at different temperatures to form titanium dioxide having different properties. The steps of the nanotubes.
优选的， 二氧化钛（Ti02)纳米管的合成是将二氧化钛 (Ti02)纳米管前驱 体置大烧杯中， 调节 pH为 2.5， 搅拌、 酸交换 2h ; 洗涤至 pH为 6〜6.5， 60 °C烘箱中烘干。将 60度烘干的二氧化钛 (Ti02)纳米管在不同温度下焙烧， 得 到不同类型的二氧化钛 (Ti02)纳米管。 其焙烧条件为： 升温速度 1度 /分， 分 别在 200〜600度下焙烧 5h。 Preferably, the titanium dioxide (Ti0 2 ) nanotube is synthesized by placing a titanium dioxide (Ti0 2 ) nanotube precursor in a large beaker, adjusting the pH to 2.5, stirring, acid exchange for 2 h, washing to pH 6 to 6.5, 60 ° C. Dry in an oven. Titanium dioxide (Ti0 2 ) nanotubes dried at 60 degrees were calcined at different temperatures to obtain different types of titanium dioxide (Ti0 2 ) nanotubes. The firing conditions were as follows: The heating rate was 1 degree/minute, and calcined at 200 to 600 degrees for 5 hours.
优选的， 所述方法步骤 （2 ) 中对合成的二氧化钛纳米管进行表征的方 法包括采用透射电镜、 BET比表面积、 X射线衍射方法对二氧化钛纳米管进 行表征。  Preferably, the method for characterizing the synthesized titanium dioxide nanotubes in the method step (2) comprises characterizing the titanium dioxide nanotubes by transmission electron microscopy, BET specific surface area, and X-ray diffraction.
优选的， 所述方法步骤 （2 ) 中采用透射电镜方法表征具备光催化活性 的二氧化钛纳米管管径在 l Onm左右， 管壁 3~4层。  Preferably, in the method step (2), the TiO 2 nanotubes having photocatalytic activity are characterized by a transmission electron microscope method, and the tube diameter is about 3 nm, and the tube wall is 3 to 4 layers.
优选的， 所述方法步骤 （2 ) 中采用 X射线衍射方法表征具备光催化活 性的二氧化钛纳米管在低于 400 °C焙烧温度的纳米管为钛酸型， 高于 400 Ό 的纳米管烧为二氧化钛锐钛矿型。  Preferably, in the method step (2), the X-ray diffraction method is used to characterize the photocatalytic activity of the titanium dioxide nanotubes, and the nanotubes having a calcination temperature lower than 400 ° C are titanate type, and the nanotubes above 400 烧 are burned. Titanium dioxide anatase type.
优选的， 所述方法步骤 （3 ) 中测定不同条件下二氧化钛纳米管对模拟 污染物的吸附、光降解率包括测定不同焙烧温度下所得二氧化钛纳米管对模 拟污染物亚甲基蓝的吸附、 光降解率。  Preferably, in the method step (3), the adsorption and photodegradation rate of the simulated pollutants by the titanium dioxide nanotubes under different conditions are determined, and the adsorption and photodegradation rates of the simulated contaminant methylene blue by the obtained titanium dioxide nanotubes at different calcination temperatures are determined.
所述步骤 （3 ) 中测定不同类型二氧化钛 (T )2)纳米管对模拟污染物亚 甲基蓝（MB)的吸附 -降解性能评测是通过研究吸附等温线、 光降解曲线、 降 解率及动力学研究进行的。其中亚甲基蓝（MB)在二氧化钛（Ti02)纳米管上的 吸附等温线符合 Langmuir吸附模型。 而通过光降解曲线、 降解率的研究确 定 400 Ό焙烧温度下所得的二氧化钛（Ti02)纳米管对模拟污染物亚甲基蓝 (MB)的吸附-降解效果最好， 其降解率可达 85%。 本发明通过动力学研究， 反映出二氧化钛（Ti02)纳米管对模拟污染物亚甲基蓝（MB)的光降解是个综 合过程， 同时受吸附和表面光解两个过程的影响。 二氧化钕 (Ti02)纳米管先 吸附模拟污染物亚甲基蓝 (MB) , 然后在表面降解。 In the step (3), the adsorption-degradation performance of the different types of titanium dioxide (T) 2 nanotubes on the simulated pollutant methylene blue (MB) was evaluated by studying adsorption isotherms, photodegradation curves, degradation rates and kinetic studies. of. The adsorption isotherm of methylene blue (MB) on titanium dioxide (Ti0 2 ) nanotubes accords with the Langmuir adsorption model. Through the study of photodegradation curve and degradation rate, it is determined that the titanium dioxide (Ti0 2 ) nanotubes obtained at the calcination temperature of 400 Ό have the best adsorption-degradation effect on the simulated pollutant methylene blue (MB), and the degradation rate can reach 85%. The kinetic study of the present invention reflects that the photodegradation of the simulated pollutant methylene blue (MB) by titanium dioxide (Ti0 2 ) nanotubes is a comprehensive process, and is affected by both adsorption and surface photolysis processes. The cerium oxide (Ti0 2 ) nanotubes first adsorb the simulated contaminant methylene blue (MB) and then degrade on the surface.
相对于现有技术中的方案， 本发明的优点是- 1、 本发明技术方案通过透射电镜（TEM)、 BET比表面积、 X射线衍射 (XRD)对其进行了表征， 通过研究不同类型二氧化钛 (Ti02)纳米管对模拟污 染物亚甲基蓝 (MB)的吸附等温线、 光降解曲线、 降解率及动力学研究， 提供 了一种有效的评定二氧化钛 (Ti02)纳米管的吸附-降解性能评测方法，为二氧 化钕 (Τί02)纳米管产品的去污能力评价方法的标准化制定提供技术支持。 The advantage of the present invention over the prior art solutions is - 1. The technical scheme of the present invention is characterized by transmission electron microscopy (TEM), BET specific surface area, X-ray diffraction (XRD), and adsorption isotherm of simulated pollutant methylene blue (MB) by studying different types of titanium dioxide (Ti02) nanotubes. Wire, photodegradation curve, degradation rate and kinetics study provide an effective method for evaluating the adsorption-degradation performance of titanium dioxide (Ti0 2 ) nanotubes, which is the decontamination ability of cerium oxide (Τί0 2 ) nanotube products. Technical support is provided for the standardization of evaluation methods.
2、 本发明的测定方法可以得到二氧化钛 (Ti02)纳米管的最佳吸附 -降解 性能，通过吸附 -降解性能的优化研究可以得到二氧化钛 (Ti02)纳米管的最佳 合成条件。通过本发明测定方法所合成的二氧化钛纳米管对亚甲基蓝有较好 的吸附作用， 可有效牵制染料的迁移； 纳米管在实验条件下对亚甲基蓝有很 好的光降解作用。 在实际织物及环境水体中， 纳米管将会有效降解各种污染 物， 达到净化的作用。 2, a measuring method of the present invention can be best adsorbed titanium oxide (Ti0 and 2) nanotubes - degradation by adsorption - the optimum conditions can be obtained titanium oxide (Ti0 and 2) optimization of nanotubes of degradation. The titanium dioxide nanotubes synthesized by the method of the invention have good adsorption effect on methylene blue, and can effectively inhibit the migration of dyes; the nanotubes have good photodegradation effect on methylene blue under the experimental conditions. In the actual fabric and environmental water, the nanotubes will effectively degrade various pollutants and achieve purification.
综上所述， 本发明提供了一种基于探索产品中纳米二氧化钛 (Ti02)的微 界面性能评价的考虑， 以二氧化钛 (Ti02)自制纳米管前驱体， 酸洗、 烘干后 在不同温度下分步焙烧， 得到不同晶型二氧化钛 (Ti02)纳米管， 采用透射电 镜（TEM)、 BET比表面积、 X射线衍射（XRD)对其进行表征， 通过二氧化钛 (Ti02)纳米管对亚甲基蓝（MB)的吸附-降解性能评测， 为评价方法的标准化 制定提供技术支持。 附图说明 In summary, the present invention provides a method for evaluating the micro-interface properties of nano-titanium dioxide (Ti0 2 ) based on the exploration product, and the nanotube precursor is prepared by using titanium dioxide (Ti0 2 ), pickling and drying at different temperatures. The sub-step calcination was carried out to obtain different titania (Ti0 2 ) nanotubes, which were characterized by transmission electron microscopy (TEM), BET specific surface area, X-ray diffraction (XRD), and methylene blue by titanium dioxide (Ti0 2 ) nanotubes. MB) Adsorption-degradation performance evaluation, providing technical support for the standardization of evaluation methods. DRAWINGS
下面结合附图及实施例对本发明作进一步描述：  The present invention is further described below in conjunction with the accompanying drawings and embodiments:
图 1为 酸洗 60 °C烘干后二氧化钛（Ti02)纳米管的透射电镜（TEM)图； 图 2为 酸洗 60 °C烘干 300 °C焙烧后二氧化钛（Ti02)纳米管的透射电镜 (TEM)图； Figure 1 is a transmission electron microscope (TEM) FIG titania (Ti0 and 2) nanotubes pickling and drying 60 ° C; FIG. 2 is a transmission titania (Ti0 and 2) pickling nanotubes drying 60 ° C 300 ° C calcination Electron microscopy (TEM) image;
图 3 为 酸洗 60 °C烘干 500 Ό焙烧后二氧化钛（Ti02)纳米管的透射电镜 (TEM)图； Figure 3 is a transmission electron microscope (TEM) image of titanium dioxide (Ti0 2 ) nanotubes after baking at 500 ° C for 500 C baking;
图 4为不同焙烧温度下二氧化钛 (Ti02)纳米管的 X射线衍射 (XRD)图； 图 5为不同焙烧温度二氧化钛 (Ti02)纳米管对亚甲基蓝的光降解曲线； 图 6为不同焙烧温度二氧化钛 (Ti02)纳米管对模拟污染物亚甲基蓝 (MB) 的降解率； 4 is calcined at different temperatures titania X-ray diffraction (Ti0 2) nanotubes (XRD) pattern; FIG. 5 is a different firing temperature of titanium dioxide (Ti0 2) nanotubes to blue light degradation methylene curve; FIG. 6 is a different firing temperature of titanium dioxide (Ti0 2 ) the degradation rate of nanotubes to the simulated pollutant methylene blue (MB);
图 7 为不同焙烧温度下的模拟污染物亚甲基蓝 (MB)在二氧化钛 (Ti02) 纳米管上的吸附等温线。 具体实施方式 Figure 7 shows the simulated contaminant methylene blue (MB) in titanium dioxide (Ti0 2 ) at different calcination temperatures. Adsorption isotherms on nanotubes. detailed description
以下结合具体实施例对上述方案做进一步说明。 应理解， 这些实施例是 用于说明本发明而不限于限制本发明的范围。实施例中采用的实施条件可以 根据具体厂家的条件做进一步调整， 未注明的实施条件通常为常规实验中的 条件。  The above scheme will be further described below in conjunction with specific embodiments. It is to be understood that the examples are intended to illustrate the invention and not to limit the scope of the invention. The implementation conditions employed in the examples can be further adjusted according to the conditions of the specific manufacturer, and the unspecified implementation conditions are usually the conditions in the conventional experiment.
实施例 二氧化钛 (Ti02)纳米管对模拟污染物亚甲基蓝（MB)微界面吸附 -降解性能的测定 Determination of Micro-interface Adsorption-Degradation Performance of Simulated Contaminant Methylene Blue (MB) by Titanium Dioxide (Ti0 2 ) Nanotubes
(1) 二氧化钛 (Ti02)纳米管合成 (1) Synthesis of titanium dioxide (Ti0 2 ) nanotubes
仪器与试剂：  Instruments and reagents:
Philips Tecnai-12 型透射电子显微镜（HRTEM); D/max-RA型 X射线衍 射仪（RigaKuTM， JP); Cary 5000型 UV-VIS分光光度计（VarianTM， USA); 氢氧化钠（NaOH)(A.R.); 二氧化钛（Τί02)等。 Philips Tecnai-12 transmission electron microscope (HRTEM); D/max-RA type X-ray diffractometer (RigaKu TM , JP); Cary 5000 UV-VIS spectrophotometer (Varian TM , USA); sodium hydroxide (NaOH) ) (AR) ; titanium dioxide (Τί0 2 ) and the like.
测定条件  Measuring condition
X射线衍射 (XRD)测定条件： 起始角： 5; 终止角： 70; 步长： 0.02; 扫 描速度： 10; 积分时间： 0.1; 靶型： Cu; 管流管压： 50Kvl50mA; 狭缝： 1, 1， 0.6, 0.6； 滤波片： Graphite。 UV- Vis分光光度计测定波长： 665 nm。  X-ray diffraction (XRD) measurement conditions: Starting angle: 5; End angle: 70; Step size: 0.02; Scanning speed: 10; Integration time: 0.1; Target type: Cu; Tube pressure: 50 Kvl 50 mA; 1, 1, 0.6, 0.6; Filter: Graphite. UV-Vis spectrophotometer measured wavelength: 665 nm.
合成步骤  Synthesis step
二氧化钛（Ti02)纳米管前驱体的合成 取 16gNaOH加入 40ml蒸馏水， 完全溶解后， 取 Ti022g， 室温下搅拌 2h， 放入烘箱 150°C， 加热 5h后取出。 冷却， 将得到的块状物捣碎。 继续放入烘箱中 150 °C加热 10h。 取出冷却， 搅拌均勾， 继续放入反应釜中， 150 °C加热两天。 冷却后， 釜中下部为比较 松散的糊状物， 倒掉上清液， 得到二氧化钛 (Ti02)纳米管前驱体。 Synthesis of Titanium Dioxide (Ti0 2 ) Nanotube Precursor 16 g of NaOH was added to 40 ml of distilled water. After completely dissolving, Ti0 2 2 g was taken , stirred at room temperature for 2 h, placed in an oven at 150 ° C, and heated for 5 h before being taken out. After cooling, the resulting cake was chopped. Continue to heat in an oven at 150 °C for 10 h. Take out the cooling, stir and hook, continue to put in the reaction kettle, and heat at 150 °C for two days. After cooling, the lower part of the kettle was a relatively loose paste, and the supernatant was decanted to obtain a titanium dioxide (Ti0 2 ) nanotube precursor.
二氧化钛 (Ti02)纳米管的合成 将二氧化钛（Ti02)纳米管前驱体大烧杯 中， 调节 pH为 2.5， 搅拌、 酸交换 2h; 洗涤至 pH为 6〜6.5, 60Ό烘箱中烘 干。 将 60度烘干的纳米管在不同温度下焙烧， 得到不同性质的催化剂。 焙 烧条件为： 升温速度 1度 /分， 分别在 200〜600度下焙烧 5h。 Synthesis of titania (Ti0 2) of titanium dioxide nanotubes (Ti0 2) nanotube precursor in a large beaker, pH was adjusted to 2.5, with stirring, nucleotide exchange 2H; until the pH was 6~6.5, 60Ό drying oven. The 60-degree dried nanotubes are calcined at different temperatures to obtain catalysts of different properties. The baking conditions were as follows: the heating rate was 1 degree/minute, and the firing was performed at 200 to 600 degrees for 5 hours.
(2) 表征二氧化钛（Τί02)纳米管 (2) Characterizing titanium dioxide (Τί0 2 ) nanotubes
透射电镜（ΤΕΜ) 由 TEM图可以看出管的管径在 lOnm左右， 为纳米级， 管壁 3~4层。 Transmission electron microscope (ΤΕΜ) It can be seen from the TEM image that the tube diameter is about 1 nm, which is nanometer, and the wall is 3 to 4 layers.
BET比表面积  BET specific surface area
表 1 不同焙烧温度下二氧化钛（Ti02)纳米管的 BET比表面积 焙烧温度 /°c 未焙烧 200 300 350 400 500 600 700 比表面积 /m2*g-l 263.5 250.0 256.1 284.9 193.8 83.8 53.5 22.6 表中数据显示二氧化钛（Ti02)纳米管的 BET比表面积与焙烧温度的关 系， 基本上是随着焙烧温度的增大， 比表面积减小， 这在高温区比较明显。 此外， 对原料二氧化钛进行处理制成纳米管， 其 BET比表面积相对增大很多 (原料的 Ti02比表面积不到 10 m2， g-l )。 比表面积的增大， 对于染料分子 的吸附将更为有效。 Table 1 BET specific surface area calcination temperature of titanium dioxide (Ti0 2 ) nanotubes at different calcination temperatures / ° c Unbaked 200 300 350 400 500 600 700 specific surface area / m 2 * gl 263.5 250.0 256.1 284.9 193.8 83.8 53.5 22.6 The data in the table shows The relationship between the BET specific surface area of the titanium dioxide (Ti0 2 ) nanotubes and the calcination temperature is basically that the specific surface area decreases as the calcination temperature increases, which is more remarkable in the high temperature region. In addition, the raw material titanium dioxide is processed to form a nanotube, and its BET specific surface area is relatively increased (the Ti0 2 specific surface area of the raw material is less than 10 m 2 , gl ). The increase in specific surface area will be more effective for the adsorption of dye molecules.
X射线衍射（XRD)  X-ray diffraction (XRD)
由图 2可知， 低于 400 Ό焙烧温度的二氧化钛（Ti02)纳米管为钛酸型， 高于 400 °C的二氧化钛（Ti02)纳米管为锐钛矿型， 400 °C是二氧化钛（Ti02)纳 米管的晶变点。 Figure 2 shows, the firing temperature is lower than 400 Ό titanium oxide (Ti0 and 2) titanate nanotubes type, above 400 ° C titanium dioxide (Ti0 and 2) nanotube anatase, 400 ° C is titanium dioxide (Ti0 and 2 ) The crystallographic point of the nanotube.
( 3 ) 不同类型二氧化钛 (Ti02)纳米管对模拟污染物亚甲基蓝（MB)的吸 附 -降解 (3) Adsorption-degradation of simulated pollutant methylene blue (MB) by different types of titanium dioxide (Ti0 2 ) nanotubes
1 ) 二氧化钛（Ti02)纳米管对模拟污染物亚甲基蓝 (MB)的吸附等温线 由图 7可以看出，模拟污染物亚甲基蓝 (MB)在二氧化钛 (Τί02)纳米管上 的吸附等温线符合 Langmuir吸附模型， 即二氧化钛 (Ti02)纳米管对模拟污染 物亚甲基蓝（MB)的吸附在低浓度时达到饱和， 以后随着平衡浓度增大， 亚甲 基蓝（MB)饱和吸附量基本不变。 300 'C焙烧的二氧化钛（Ti02)纳米管对亚甲 基蓝（MB)饱和吸附量为 130mg/g。 1) The adsorption isotherm of titanium dioxide (Ti0 2 ) nanotubes on the simulated pollutant methylene blue (MB) can be seen from Figure 7. The adsorption isotherm of the simulated pollutant methylene blue (MB) on the titanium dioxide (Τί0 2 ) nanotubes is consistent with Langmuir. The adsorption model, that is, the adsorption of the simulated pollutant methylene blue (MB) by titanium dioxide (Ti0 2 ) nanotubes reaches saturation at a low concentration, and then the saturated adsorption amount of methylene blue (MB) is basically unchanged as the equilibrium concentration increases. The 300 'C calcined titanium dioxide (Ti0 2 ) nanotubes had a saturated adsorption capacity for methylene blue (MB) of 130 mg/g.
从图中也可以看出， 较低焙烧温度范围下， 二氧化钛 (Ti02)纳米管对亚 甲基蓝 (MB)的饱和吸附量随温度增大而增大； 在较高焙烧温度范围， 随着焙 烧温度的升高， 二氧化钛 (Ti02)纳米管对亚甲基蓝 (MB)吸附量明显下降。 除 了没有焙烧的二氧化钛 (Ti02)纳米管， 其它焙烧温度下二氧化钛 (Ti02)纳米 管的亚甲基蓝（MB)吸附量与表中 BET比表面积数据有较好的相关性，即二氧 化钛（Τί02)纳米管比表面积越大， 亚甲基蓝（MB)吸附量越大。 It can also be seen from the figure that the saturated adsorption amount of methylene blue (MB) on titanium dioxide (Ti0 2 ) nanotubes increases with increasing temperature at lower calcination temperature range; at higher calcination temperature range, with calcination temperature The increase in the amount of methylene blue (MB) adsorbed by titanium dioxide (Ti0 2 ) nanotubes is significantly reduced. Except that no calcination of titanium dioxide (Ti0 2) nanotube, methylene blue other firing temperature (Ti0 2) nanotubes of titanium dioxide (MB) adsorption amount table BET specific surface area data has a good correlation, i.e., titanium dioxide (Τί0 2) The larger the specific surface area of the nanotube, the larger the amount of methylene blue (MB) adsorbed.
2 ) 二氧化钛（Ti02)纳米管对模拟污染物亚甲基蓝 (MB)的光降解 模拟污染物亚甲基蓝（MB)的初始浓度为 83mg/L。 图 5可以看出 400 °C 焙烧条件下所得二氧化钛（Ti02)纳米管对模拟污染物亚甲基蓝（MB)的降解 效果最好， 降解率可达 85% , 说明二氧化钛（Ti02)纳米管作为模拟污染物亚 甲基蓝 (MB)的光降解媒质的有效性。 2) Photodegradation of simulated contaminant methylene blue (MB) by titanium dioxide (Ti0 2 ) nanotubes The initial concentration of the simulated contaminant methylene blue (MB) was 83 mg/L. Figure 5 shows that the titanium dioxide (Ti0 2 ) nanotubes obtained at 400 °C calcination have the best degradation effect on the simulated pollutant methylene blue (MB), and the degradation rate can reach 85%, indicating that the titanium dioxide (Ti0 2 ) nanotubes are used as a simulation. The effectiveness of the photodegradable medium of the contaminant methylene blue (MB).
3 ) 二氧化钛（Ti02)纳米管对模拟污染物亚甲基蓝（MB)降解动力学研究 三个焙烧温度下纳米管光降解 MB的动力学数据 焙烧温度 /°c 300 °C 400 °C 500 °C  3) Kinetics of degradation of methylene blue (MB) by simulated titanium dioxide (Ti02) nanotubes Photodynamic degradation of nanotubes at three calcination temperatures Kinetic data of MB Calcination temperature / °c 300 °C 400 °C 500 °C
速度常数 0.36 1.93 2.38  Speed constant 0.36 1.93 2.38
吸附常数 1.16 0.45 0.08  Adsorption constant 1.16 0.45 0.08
由该表结合上面的吸附图和光降解图， 反映出二氧化钛 (Ti02)纳米管作 为模拟污染物亚甲基蓝 (MB)的光降解是个综合过程，即同时受吸附和表面光 解影响。二氧化钛 (Ti02)纳米管先吸附模拟污染物亚甲基蓝 (MB)后在表面降 解。 二氧化钛 (Ti02)纳米管的比表面积越大、 孔分布越均勾， 则第一步对模 拟污染物亚甲基蓝 (MB)的吸附量越大； 同时 400 Ό以上焙烧所得的二氧化钛 (Ti02)纳米管为锐钛矿晶型， 锐钛矿对于污染物的降解相对于其它晶型更有 效， 表 2也反映出二氧化钛 (1 02)纳米管锐钛矿晶型比例越高， 对模拟污染 物亚甲基蓝（MB)的光降解速率常数越大。综合评定显示，采用亚甲基蓝 (MB) 为模拟污染物对二氧化钛（Ti02)纳米管进行微界面效应的吸附 -降解评测是 有效的， 同时发现锐钛矿型纳米管二氧化钛 (Ti02)纳米管对模拟污染物亚甲 基蓝（MB)的降解效率最好， 可达 85%。 From the table combined with the above adsorption map and photodegradation map, it is reflected that the photodegradation of titanium dioxide (Ti0 2 ) nanotubes as a simulated pollutant methylene blue (MB) is a comprehensive process, which is affected by both adsorption and surface photolysis. The titanium dioxide (Ti0 2 ) nanotubes first adsorbed the surface of the simulated pollutant methylene blue (MB) and degraded on the surface. The larger the specific surface area of the titanium dioxide (Ti0 2 ) nanotubes and the more uniform the pore distribution, the larger the adsorption amount of the simulated pollutant methylene blue (MB) in the first step; and the titanium dioxide (Ti0 2 ) nanometer obtained by calcining more than 400 Ό. The tube is anatase crystal form, and the degradation of contaminants by anatase is more effective than other crystal forms. Table 2 also reflects that the higher the proportion of titanium dioxide (1 0 2 ) nanotube anatase crystal form, the simulated pollutants The photodegradation rate constant of methylene blue (MB) is larger. The comprehensive evaluation showed that the adsorption-degradation evaluation of the micro-interface effect of titanium dioxide (Ti0 2 ) nanotubes using methylene blue (MB) as a simulated pollutant was effective, and anatase-type nanotube titanium dioxide (Ti0 2 ) nanotube pairs were also found. The simulated pollutant methylene blue (MB) has the best degradation efficiency, up to 85%.
本实施例以亚甲基蓝（MB)为模拟污染物对应用较广的二氧化钛（Ti02) 纳米材料进行微界面效应的吸附 -降解研究， 以二氧化钛 (Τί02)自制纳米管前 驱体， 酸洗、 烘干后在不同温度下分步焙烧， 得到不同晶型二氧化钛 (Ti02) 纳米管， 采用透射电镜（TEM)、 BET比表面积、 X射线衍射（XRD)对其进行 表征， 通过二氧化钛（Ti02)纳米管对模拟污染物亚甲基蓝（MB)的吸附等温 线、 光降解曲线、 降解率及动力学研究， 计算染料亚甲基蓝 (MB)光催化反应 的降解率， 以此来评价该材料的吸附、 光降解性能。 In this embodiment, the adsorption-degradation of the widely used titanium dioxide (Ti0 2 ) nanomaterials by using methylene blue (MB) as a simulated pollutant is studied, and the nanotube precursor is prepared by titanium dioxide (Τί0 2 ), pickled and baked. After drying, the calcination was carried out at different temperatures to obtain different titania (Ti0 2 ) nanotubes, which were characterized by transmission electron microscopy (TEM), BET specific surface area and X-ray diffraction (XRD), and passed through titanium dioxide (Ti0 2 ). The adsorption isotherms, photodegradation curves, degradation rates and kinetics of the simulated pollutant methylene blue (MB) were calculated by nanotubes. The degradation rate of the photocatalytic reaction of the dye methylene blue (MB) was calculated to evaluate the adsorption and photodegradation of the material. performance.
实验所用二氧化钛（Ti02)纳米管对模拟污染物亚甲基蓝（MB)有较好的 吸附作用， 最高吸附量可达 130mg/g ; 二氧化钛（Ti02)纳米管在实验条件下 对模拟污染物亚甲基蓝 (MB)有很好的光降解作用， 最高降解率可达 85%。 研究表明， 通过对二氧化钛（Ti02)纳米材料对模拟污染物亚甲基蓝（MB)的微 界面效应的吸附-降解性能评测， 可适用于生产加工能赋予产品抗菌、 防霉、 净化空气、 表面自清洁等特殊功效的纳米材料性能品质测试评定， 有利于为 进一步完善纳米产品技术的标准提供相应的技术支撑。 The titanium dioxide (Ti0 2 ) nanotubes used in the experiment have a good adsorption effect on the simulated pollutant methylene blue (MB), and the highest adsorption capacity can reach 130 mg/g. The titanium dioxide (Ti0 2 ) nanotubes under the experimental conditions simulate the pollutant methylene blue ( MB) has good photodegradation and the highest degradation rate is 85%. Studies have shown that the adsorption-degradation performance evaluation of the micro-interface effect of titanium dioxide (Ti0 2 ) nanomaterials on the simulated pollutant methylene blue (MB) can be applied to the production process to impart antibacterial, anti-mildew, air purification and surface self-cleaning. The evaluation of the performance and quality of nano-materials with special effects is conducive to providing corresponding technical support for further improving the standards of nano-product technology.
上述实例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技 术的人是能够了解本发明的内容并据以实施， 并不能以此限制本发明的保护 范围。 凡根据本发明精神实质所做的等效变换或修饰， 都应涵盖在本发明的 保护范围之内。  The above examples are only intended to illustrate the technical concept and the features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the present invention and to implement the present invention, and the scope of the present invention is not limited thereto. Equivalent transformations or modifications made in accordance with the spirit of the invention are intended to be included within the scope of the invention.

Claims

权 利 要 求 书 Claims
1 - 一种二氧化钛纳米管微界面的吸附-降解性能测定方法， 其特征在于 所述方法包括以下步骤： 1 - A method for determining the adsorption-degradation performance of a micro interface of a titanium dioxide nanotube, characterized in that the method comprises the following steps:
( 1 ) 遴选合适的模拟污染物；  (1) selecting suitable simulated pollutants;
( 2 ) 合成二氧化钛纳米管以及对合成的二氧化钛纳米管进行表征； (2) synthesizing titanium dioxide nanotubes and characterizing the synthesized titanium dioxide nanotubes;
( 3 )测定不同条件下二氧化钛纳米管对模拟污染物的吸附、 光降解率。 (3) Determination of adsorption and photodegradation rate of simulated pollutants by titanium dioxide nanotubes under different conditions.
2、 根据权利要求 1所述的方法， 其特征在于所述方法步骤 （1 ) 中模拟 污染物选自亚甲基蓝。  2. A method according to claim 1 wherein the simulated contaminant in step (1) of the method is selected from the group consisting of methylene blue.
3、 根据权利要求 1所述的方法， 其特征在于所述方法步骤 （2 ) 中二氧 化钛纳米管的合成包括形成二氧化钛纳米管前驱体的步骤和二氧化钛纳米 管前驱体合成二氧化钛纳米管的步骤。  The method according to claim 1, characterized in that the synthesis of the titanium dioxide nanotubes in the method step (2) comprises the steps of forming a titanium dioxide nanotube precursor and synthesizing the titanium dioxide nanotubes with the titanium dioxide nanotube precursor.
4、 根据权利要求 3所述的方法， 其特征在于所述方法步骤 （2 ) 中二氧 化钛纳米管前驱体的形成步骤包括二氧化钛在反应釜内以水溶液为反应介 质， 经强碱处理， 加热溶解， 冷却结晶形成。  4. The method according to claim 3, wherein the step of forming the titanium dioxide nanotube precursor in the step (2) of the method comprises: using titanium dioxide in the reaction vessel as an reaction medium, treating with a strong alkali, heating and dissolving, Cooling crystal formation.
5、 根据权利要求 3所述的方法， 其特征在于所述方法步骤 （2 ) 中二氧 化钛纳米管前驱体合成二氧化钛纳米管的步骤包括将二氧化钛纳米管前驱 体酸洗至 pH为 6〜6.5烘干在不同温度条件下焙烧形成不同性质的二氧化钛 纳米管的步骤。  5. The method according to claim 3, wherein the step of synthesizing the titanium dioxide nanotubes in the titanium dioxide nanotube precursor in the method step (2) comprises pickling the titanium dioxide nanotube precursor to a pH of 6 to 6.5. The step of firing to form titanium dioxide nanotubes of different properties under different temperature conditions.
6、 根据权利要求 1所述的方法， 其特征在于所述方法步骤 （2 ) 中对合 成的二氧化钛纳米管进行表征的方法包括采用透射电镜、 BE T比表面积、 X 射线衍射方法对二氧化钛纳米管进行表征。  6. The method according to claim 1, wherein the method for characterizing the synthesized titanium dioxide nanotubes in the method step (2) comprises using a transmission electron microscope, a BE T specific surface area, and an X-ray diffraction method for the titanium dioxide nanotubes. Characterize.
7、 根据权利要求 6所述的方法， 其特征在于所述方法步骤 （2 ) 中釆用 透射电镜方法表征具备光催化活性的二氧化钛纳米管管径在 lOnm左右， 管 壁 3~4层。  7. The method according to claim 6, characterized in that in the method step (2), the diameter of the titanium dioxide nanotubes having photocatalytic activity is about lOnm and the walls of the tubes are 3 to 4 layers by means of transmission electron microscopy.
8、 根据权利要求 6所述的方法， 其特征在于所述方法步骤 （2 ) 中采用 X射线衍射方法表征具备光催化活性的二氧化钕纳米管在低于 400Ό焙烧温 度的纳米管为钛酸型， 高于 400Ό的纳米管烧为二氧化钛锐钛矿型。  8. The method according to claim 6, characterized in that in the method step (2), the photocatalytic activity of the ceria nanotubes having a photocatalytic activity at a calcination temperature of less than 400 Å is determined by an X-ray diffraction method. Type, the nanotubes above 400 烧 are burnt to the titanium dioxide anatase type.
9、 根据权利要求 6所述的方法， 其特征在于所述方法步骤 （3 ) 中测定 不同条件下二氧化钕纳米管对模拟污染物的吸附、光降解率包括测定不同焙 烧温度下所得二氧化钛纳米管对模拟污染物亚甲基蓝的吸附、 光降解率。  9. The method according to claim 6, characterized in that in the method step (3), the adsorption and photodegradation rate of the simulated pollutants by the ceria nanotubes under different conditions are determined, and the obtained titanium dioxide nanometers at different calcination temperatures are determined. The adsorption and photodegradation rate of the simulated pollutant methylene blue.
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CN111569785A (en) * 2020-03-25 2020-08-25 南京延长反应技术研究院有限公司 Immersed propylene hydration micro-interface enhanced reaction system and process
CN111569784A (en) * 2020-03-25 2020-08-25 南京延长反应技术研究院有限公司 Sectional type intensified reaction system and process for preparing isopropanol by propylene hydration

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