WO2019085532A1 - Composite material of trivalent titanium self-doped titanium dioxide nanoparticles-partially reduced graphene oxide nanosheets and preparation method therefor - Google Patents

Composite material of trivalent titanium self-doped titanium dioxide nanoparticles-partially reduced graphene oxide nanosheets and preparation method therefor Download PDF

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WO2019085532A1
WO2019085532A1 PCT/CN2018/093954 CN2018093954W WO2019085532A1 WO 2019085532 A1 WO2019085532 A1 WO 2019085532A1 CN 2018093954 W CN2018093954 W CN 2018093954W WO 2019085532 A1 WO2019085532 A1 WO 2019085532A1
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graphene oxide
titanium dioxide
self
composite material
trivalent
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PCT/CN2018/093954
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French (fr)
Chinese (zh)
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赖跃坤
王姗迟
王晓沁
黄剑莹
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南通纺织丝绸产业技术研究院
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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B01J35/39—
    • B01J35/393—
    • B01J35/396—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing

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  • the invention relates to the field of composite materials, in particular to a preparation method of a trivalent titanium self-doped titanium dioxide nanoparticle-partially reduced graphene oxide nanosheet composite material and a composite material prepared.
  • multiphase photocatalysts are valued by many researchers, can absorb radiation, convert solar energy into electrical energy or chemical energy, and thus can be effectively applied to many places, such as photodegradation of organic pollutants, solar water decomposing hydrogen production , dye-sensitized solar cells and Carbon monoxide photoreduction, addition, all of these applications are low cost, high efficiency, easy to use features.
  • Titanium dioxide (TiO 2 ), a novel semiconductor material, is widely used for photocatalytic degradation of organic pollutants, gas sensors, dye-sensitized solar cells, biomaterials, and photolysis of hydrogen, and its low cost, good mechanical properties, bio-phase Good compatibility, compared with other semiconductor photocatalytic materials, TiO 2 has the advantages of biological and chemical inertness, strong oxidizing ability, non-toxicity and less prone to photochemical corrosion, and has become the most extensive research on photocatalysts.
  • Graphene is a two-dimensional material which has been discovered in recent years and is a graphite sheet which is closely packed with carbon atoms and has a honeycomb structure. Its special structure makes it have a high specific surface area, excellent thermal conductivity and excellent performance. Its electron transport capability and good adsorption performance make it ideal for developing high performance composite materials.
  • the object of the present invention is to provide a trivalent titanium self-doped titanium dioxide nanoparticle-partially reduced graphene oxide nanosheet composite material having excellent visible light catalytic performance.
  • the technical solution of the present invention is: a trivalent titanium self-doped titanium dioxide nanoparticle-partially reduced graphene oxide nanosheet composite material, the composite material being in the form of a powder, the powder particles comprising a portion as a substrate
  • the graphene oxide nanosheet is reduced and the trivalent titanium self-doped titanium dioxide nanoparticle as a support is uniformly deposited on the partially reduced graphene oxide nanosheet.
  • the invention also provides another technical solution: a preparation method of a trivalent titanium self-doped titanium dioxide nanoparticle-partially reduced graphene oxide nanosheet composite material, comprising the following steps:
  • the mass ratio of the graphene oxide powder to the titanium dioxide precursor is 1:5-1:2;
  • Step (1) and step (2) have no order.
  • the graphite is converted into a graphene oxide solution by a hummer method, and the graphene oxide solution is sequentially obtained by centrifugal washing and lyophilization to obtain the graphene oxide powder.
  • the graphene oxide powder has a mass of 0.1 g to 0.3 g
  • the titania precursor is tetrabutyl titanate
  • the tetrabutyl titanate has a volume of 0.3 ml to 0.8 ml.
  • the solvent A includes anhydrous ethanol and deionized water, wherein the volume ratio of anhydrous ethanol to deionized water is 200:1-250:1, in the step (1), the first step is The graphene oxide powder is dissolved in the anhydrous ethanol, and then the deionized water is added to the solution of the graphene oxide powder and the anhydrous ethanol, and the mass ratio of the graphene oxide powder to the solvent A is 1. :200-1:50.
  • the solvent B is anhydrous ethanol, and the volume ratio of the titanium dioxide precursor to the solvent B is 1:45 to 1:40.
  • the mixed solution B is added to the mixed solution A in a dropping manner while continuously stirring the mixed solution A.
  • the stirring treatment in the step (4) is ultrasonic stirring for 0.5 h to 1 h.
  • the reaction temperature of the hydrothermal treatment in the step (4) is 200 ° C - 250 ° C, and the reaction time is 9 h - 11 h.
  • the drying treatment in the step (4) is centrifugal drying.
  • the trivalent titanium self-doped titanium dioxide nanoparticle-partially reduced graphene oxide nanosheet composite material disclosed in the invention the self-doping of trivalent titanium introduces a gap state in the titanium dioxide band gap, thereby solving the titanium dioxide band gap
  • the light absorption range is extended to the visible light region
  • the combination with the graphene oxide further reduces the recombination of electrons and holes, thereby improving the photocatalytic ability of the composite material for the organic dye and the hydrogen decomposition for photolysis, and
  • the photoelectric properties of the titanium dioxide/graphene composite doped with trivalent titanium are significantly improved, and the chemical stability and recyclability are good, and the trivalent titanium of the invention can be self-doped.
  • the hetero-titanium dioxide nano-particle-reduced graphene oxide nanosheet composite material has the advantages of high precision, simple process, rapid economy and the like in photocatalytic degradation of pollutants and photolysis of hydrogen.
  • the preparation method of the trivalent titanium self-doped titanium dioxide nanoparticle-partially reduced graphene oxide nanosheet composite material disclosed by the invention realizes the loading of the titanium dioxide nanoparticles on the graphene oxide nanosheet by one-step hydrothermal method
  • the self-doping of trivalent titanium and partial reduction of graphene oxide, the obtained trivalent titanium-doped titanium dioxide nanoparticles have uniform size distribution, the method is simple in operation, mild in condition, simple in process, and photocatalytic degradation of industrial organic dyes and photolysis
  • the field of water hydrogen production shows a good future.
  • Example 1 is an SEM image of a composite material prepared in Example 1 of the present invention
  • 2a is a TEM image of a composite material prepared according to Example 1 of the present invention having an enlarged size of 50 nm;
  • Example 2b is a TEM image of the composite material prepared in Example 1 of the present invention with an enlarged size of 100 nm;
  • 2d is a HRTEM image of the lattice spacing of the composite material prepared in Example 1 of the present invention.
  • Figure 3a is an EDS diagram of a composite material prepared in Example 1 of the present invention.
  • Figure 3b is a diagram showing the element distribution of the composite material prepared in Example 1 of the present invention.
  • Example 4a is a full spectrum of XPS of a simple titanium dioxide, a trivalent titanium self-doped titanium dioxide nanoparticle, and a composite prepared in Example 1 of the present invention
  • 4b is an XPS narrow spectrum diagram of Ti element corresponding to the composite material prepared in Example 1 of the present invention.
  • 4c is an XPS narrow spectrum diagram of the O element corresponding to the composite material prepared in Example 1 of the present invention.
  • 4d is an XPS narrow spectrum diagram of a C element corresponding to the composite material prepared in Example 1 of the present invention.
  • 5a is an XRD pattern of a simple titanium dioxide, a trivalent titanium self-doped titanium dioxide nanoparticle, and a composite prepared in Example 1 of the present invention
  • 5b is an enlarged XRD pattern of the 101 surface region of the simple titanium dioxide, the trivalent titanium self-doped titanium dioxide nanoparticles, and the composite material prepared in Example 1 of the present invention;
  • Figure 5c is an XRD pattern of graphene oxide
  • 6a is a Raman spectrum of a simple titanium dioxide, a trivalent titanium self-doped titanium dioxide nanoparticle, and a composite prepared in Example 1 of the present invention
  • 6b is an enlarged Raman spectrum of a peak of a simple material of titanium dioxide, trivalent titanium self-doped titanium dioxide nanoparticles, and a composite material prepared in Example 1 of the present invention at a displacement of 150 cm-1;
  • 6c is an enlarged Raman spectrum of the D, G peak of the composite material prepared by the simple titanium dioxide, the trivalent titanium self-doped titanium dioxide nanoparticle, and the inventive example 1;
  • 6d is an infrared spectrum of a simple titanium dioxide, graphene oxide, and a composite material prepared in Example 1 of the present invention
  • 7a is a UV-visible diffuse reflection spectrum of a composite material prepared by using the titanium dioxide, the trivalent titanium self-doped titanium dioxide nanoparticles, and the inventive example 1;
  • Example 7b is a photoluminescence spectrum of a simple titanium dioxide, a trivalent titanium self-doped titanium dioxide nanoparticle, and a composite prepared in Example 1 of the present invention
  • Example 7c is a photocurrent response diagram of a simple titanium dioxide, a trivalent titanium self-doped titanium dioxide nanoparticle, and a composite prepared in Example 1 of the present invention
  • Example 7d is an impedance spectrum of a simple titanium dioxide, a trivalent titanium self-doped titanium dioxide nanoparticle, and a composite material prepared in Example 1 of the present invention under illumination;
  • Example 8a is a graph showing the efficiency of degrading methylene blue under visible light conditions for a simple titanium dioxide, a trivalent titanium self-doped titanium dioxide nanoparticle, and a composite material prepared in Example 1 of the present invention;
  • Figure 8b is a graph showing the ultraviolet absorption wavelength of the composite material prepared in Example 1 of the present invention.
  • SEM image electronic scanning imaging
  • TEM image transmission electron scanning imaging
  • HRTEM image high-resolution transmission electron scanning imaging
  • SAED image selected area electron diffraction pattern
  • EDS diagram energy spectrum
  • XRD Map X-ray diffraction pattern
  • XPS spectrum X-ray photoelectron spectroscopy spectrum.
  • an embodiment or “an embodiment” as used herein refers to a particular feature, structure, or characteristic that can be included in at least one implementation of the invention.
  • the synthesized graphene oxide aqueous solution is centrifuged and then freeze-dried to obtain dried graphene oxide powder soluble in absolute ethanol, 0.1 g of graphene oxide powder is dispersed in 20 ml of absolute ethanol, and then 0.1 ml of deionized water is added to form Mixing solution A, 0.3 ml of titanium dioxide precursor tetrabutyl titanate and 20 ml of absolute ethanol are mixed to form a mixed solution B, and the mixed solution B is slowly added dropwise to the mixed solution A to form a mixed solution C, and the mixed solution C is ultrasonically stirred for 1 hour.
  • the mixed solution C was reacted at a reaction temperature of 220 ° C for 10 hours, and then centrifugally dried to obtain a trivalent titanium self-doped titanium oxide nanoparticle-partially reduced graphene oxide nanosheet composite material.
  • the above graphene oxide powder is prepared by synthesizing graphene oxide in an ice bath at 15 ° C or less, dissolving 2 g of graphite and 6 g of potassium permanganate in 46 mL of anhydrous concentrated sulfuric acid, raising the temperature to 35 ° C and stirring for 2 h, and heating up to 100 ml of water was added dropwise at 80 ° C, then the temperature was raised to 95 ° C and 300 ml of water, and 1-2 ml of anhydrous hydrogen peroxide was added dropwise.
  • the treatment conditions were lyophilized.
  • the titanium dioxide, the trivalent titanium self-doped titanium dioxide nanoparticles and the prepared composite material were respectively immersed in a methylene blue contaminated aqueous solution having an initial concentration of 40 mg/L, and stirred in a dark environment for 12 hours to reach an adsorption equilibrium state, and then in visible light.
  • the lower irradiation was 0-120 min, and the time interval was 30 min. At each time interval, the corresponding solution was used to test the ultraviolet-visible absorption value.
  • FIG. 1 is an SEM image of the prepared composite material, it can be seen that the titanium dioxide nanoparticles are uniformly deposited on the surface of the graphene nanosheet;
  • Figure 2a shows the TEM image of the composite material with a magnification of 50 nm
  • Figure 2b shows the TEM image of the composite material with a magnification of 100 nm, which further proves that the trivalent titanium self-doped titanium dioxide nanoparticles are uniformly deposited on the graphene.
  • the surface of the nanosheet, the size of the trivalent titanium self-doped titanium dioxide nanoparticles is about 6 nm;
  • FIG. 2c is a SAED diagram of the prepared composite material
  • FIG. 2d is a HRTEM image of the lattice spacing of the prepared composite material exhibiting titanium dioxide, and the TiO 2 anatase type (101) crystal plane lattice spacing is 0.35 nm;
  • Figure 3a is an EDS diagram of the prepared composite material
  • Figure 3b is an elemental distribution map of the prepared composite material, indicating that the gold-modified bismuth molybdate nanosheet/titanium dioxide nanotube array mainly contains three elements of Ti, O, and C;
  • Figure 4a shows the XPS full spectrum of the simple titanium dioxide, trivalent titanium self-doped titanium dioxide nanoparticles and the prepared composite material
  • Figure 4b shows the XPS narrow spectrum of the Ti element corresponding to the prepared composite material
  • Figure 4c shows the preparation
  • the composite material corresponds to the XPS narrow spectrum of the O element
  • Figure 4d shows the XPS narrow spectrum of the C element corresponding to the composite.
  • the peaks of the Ti, O and C elements can be clearly seen in the full spectrum of Figure 4a. From the Ti 2p high-resolution XPS narrow spectrum, the peak of trivalent titanium can be clearly seen.
  • Figure 5a shows the XRD pattern of the pure titanium dioxide, trivalent titanium self-doped titanium dioxide nanoparticles and the prepared composite material
  • Figure 5b shows the simple titanium dioxide, trivalent titanium self-doped titanium dioxide nanoparticles and the prepared composite material in 101
  • the enlarged XRD pattern of the surface region Figure 5c is the XRD pattern of graphene oxide. It can be seen that the XRD peak of the trivalent titanium self-doped titanium dioxide nanoparticles and the prepared composite material is shifted to the left relative to the XRD peak of the simple titanium dioxide.
  • Figure 6a shows the Raman spectrum of pure titanium dioxide, trivalent titanium self-doped titanium dioxide nanoparticles and the prepared composite.
  • the unmodified titanium dioxide in Figure 6a shows a typical anatase Raman spectrum.
  • a new peak position appears in the Ti 3+ doped titanium dioxide crystal, indicating that the change of the titanium dioxide structure after the reduction of Ti 3+ leads to disorder, thereby exciting the edge region of the crystal;
  • Figure 6b is an enlarged Raman spectrum of a simple titanium dioxide, trivalent titanium self-doped titanium dioxide nanoparticle and a prepared composite at a displacement of 150 cm -1
  • Figure 6c is a simple titanium dioxide, trivalent titanium self - doped titanium dioxide nanoparticle and preparation thereof
  • the magnified Raman spectra of the composites at D and G peaks clearly show the peak directions of trivalent titanium self-doped titanium dioxide nanoparticles and trivalent titanium self-doped titanium dioxide nanoparticles-partially reduced graphene oxide nanosheet composites.
  • the high displacement direction shift indicates that there is trivalent titanium doping in the composite.
  • the D peak is larger than the G peak, indicating that partial oxidation of graphene is reduced to obtain partially reduced graphene oxide, which shows that the hydrothermal reaction makes three
  • the valence titanium doping and graphene reduction are carried out simultaneously, and the proof conforms to the results of XPS and XRD analysis;
  • Figure 6d shows the infrared spectrum of simple titanium dioxide, graphene oxide and the prepared composite.
  • the graphene oxide layer contains many oxygen-containing functional groups, and the broad absorption peak appearing at 3403 cm -1 corresponds to the stretching vibration absorption peak of -OH.
  • 1626 cm -1 is a skeleton vibration peak of an unoxidized graphite region
  • a stretching vibration peak 1072 cm -1 is a stretching vibration peak of C-O in C-O-C
  • the vibration peak of the main oxygen-containing functional group of graphene oxide in the composite such as 1728 cm -1
  • the strengths of 1390cm -1 , 1238cm -1 and 1072cm -1 are obviously weakened, indicating that graphene oxide has a certain degree of reduction during hydrothermal process, but it has not been completely reduced to graphene.
  • the strong absorption peak appearing at 479 cm -1 is attributed to the stretching vibration of Ti-O-Ti, indicating that titanium dioxide and graphene oxide are better combined;
  • Figure 7a shows the UV-visible diffuse reflectance spectra of pure titanium dioxide, trivalent titanium self-doped titanium dioxide nanoparticles and composites prepared, which reflect the optical properties and different band gap structures of the prepared photocatalysts. Titanium dioxide alone absorbs only ultraviolet light, and its basic absorption edge is close to 400 nm. Compared with titanium dioxide alone, trivalent titanium self-doped titanium dioxide nanoparticles and trivalent titanium self-doped titanium dioxide nanoparticles-partially reduced graphene oxide nanosheet composites The absorption in the region between 400 and 800 nm is further increased;
  • Figure 7b shows the photoluminescence spectra of simple titanium dioxide, trivalent titanium self-doped titanium dioxide nanoparticles and composites prepared.
  • the simple titanium dioxide exhibits a high emission peak intensity, and the trivalent titanium self-doped titanium dioxide nanoparticles - partial reduction oxidation
  • the PL strength of graphene nanosheet composites is further weakened, indicating that the interface electrons are transferred from the conduction band of trivalent titanium self-doped titanium dioxide to the surface of partially reduced graphene oxide nanosheets, which reduces the recombination of electrons and holes, thereby enhancing the three Photocatalytic activity of valence titanium self-doped titanium dioxide nanoparticles-partially reduced graphene oxide nanosheet composites;
  • Fig. 7c is a photocurrent response diagram of a simple titanium dioxide, a trivalent titanium self-doped titanium dioxide nanoparticle, and a composite material prepared by using a 0.1 M anhydrous sodium sulfate as an electrolyte, and filtering a wavelength below 400 nm with a filter.
  • the photocurrent test is carried out under the three-electrode system of the CHI660D electrochemical workstation, the trivalent titanium self-doped titanium dioxide nanoparticles and the trivalent titanium self-doping
  • the photocurrent densities of the titanium dioxide nanoparticle-partially reduced graphene oxide nanosheet composites are 0.0025, 0.0046, 0.0192, and 0.0132 mA/cm 2 , respectively, which are four times the photocurrent density (0.0006 mA/cm 2 ) of the simple titanium dioxide.
  • Figure 7d shows the impedance spectrum of pure titanium dioxide, trivalent titanium self-doped titanium dioxide nanoparticles and the prepared composite under light conditions.
  • the 0.1M anhydrous sodium sulfate is used as the electrolyte, and the xenon lamp is filtered by filters below 400 nm.
  • the wavelength is simulated by visible light.
  • the distance from the light source to the beaker is 15 cm, and the light intensity is 60 mW/cm2.
  • the AC impedance test is performed under the three-electrode system of the CHI660D electrochemical workstation.
  • the AC impedance spectra of pure titanium dioxide, trivalent titanium self-doped titanium dioxide nanoparticles and trivalent titanium self-doped titanium dioxide nanoparticles-partially reduced graphene oxide nanosheet composites Compared with simple titanium dioxide, the trivalent titanium self-doped titanium dioxide nanoparticles show a smaller semicircle, indicating that effective photogenerated electron-hole separation is achieved on the trivalent titanium self-doped titanium dioxide electrode.
  • the trivalent titanium self-doped titanium dioxide nanoparticle-partially reduced graphene oxide nanosheet composite shows the smallest semi-circular arc in the AC impedance spectrum, indicating that the electron acceptor undergoes faster interfacial charge transfer after the introduction of graphene. And lead to efficient separation of electron-hole pairs;
  • Fig. 8a is a graph showing the efficiency of degrading methylene blue under visible light conditions by simple titanium dioxide, trivalent titanium self-doped titanium dioxide nanoparticles and the prepared composite material
  • Fig. 8b is a UV absorption wavelength diagram of the prepared composite material.
  • trivalent titanium self-doped titanium dioxide nanoparticles and trivalent titanium self-doped titanium dioxide nanoparticles-partially reduced graphene oxide nanosheet composites to degrade methylene blue under visible light, compared with simple titanium dioxide, trivalent
  • the degradation efficiency of methylene blue by titanium self-doped titanium dioxide is obviously improved.
  • the photodegradation of methylene blue by trivalent titanium self-doped titanium dioxide nanoparticles-partially reduced graphene oxide nanosheet composites is basically degraded at 120 min, and the degradation efficiency reaches 100%. .
  • the following is a preparation method of trivalent titanium self-doped titanium dioxide nanoparticle-partially reduced graphene oxide nanosheet composite material: the synthesized graphene oxide aqueous solution is centrifugally washed and freeze-dried to obtain dried graphite oxide soluble in absolute ethanol.
  • the olefin powder, 0.2 g of graphene oxide powder is dispersed in 20 ml of absolute ethanol, 0.1 ml of deionized water is further added to form a mixed solution A, and 0.5 ml of a titanium dioxide precursor tetrabutyl titanate is formed into a mixed solution with 20 ml of absolute ethanol.
  • the mixed solution B mixed solution was slowly added dropwise to the mixed solution A to form a mixed solution C, and the mixed solution C was ultrasonically stirred for 1 hour, and then the mixed solution C was reacted at a reaction temperature of 220 ° C for 10 hours, followed by centrifugation and drying to obtain Trivalent titanium self-doped titanium dioxide nanoparticles-partially reduced graphene oxide nanosheet composite.
  • the following is a preparation method of trivalent titanium self-doped titanium dioxide nanoparticle-partially reduced graphene oxide nanosheet composite material: the synthesized graphene oxide aqueous solution is centrifugally washed and freeze-dried to obtain dried graphite oxide soluble in absolute ethanol. Alkenes, 0.3 g of graphene oxide powder was dispersed in 20 ml of absolute ethanol, then 0.1 ml of deionized water was added to form a mixed solution A, and 0.8 ml of a titanium dioxide precursor tetrabutyl titanate and 20 ml of absolute ethanol were mixed to form a mixed solution B.
  • the mixed solution B was slowly added dropwise to the mixed solution A to form a mixed solution C, and the mixed solution C was ultrasonically stirred for 1 h, and then the mixed solution C was hydrothermally reacted at a reaction temperature of 220 ° C for 10 h, and then centrifuged to obtain three Titanium self-doped titanium dioxide nanoparticles-partially reduced graphene oxide nanosheet composites.

Abstract

A composite material of trivalent titanium self-doped titanium dioxide nanoparticles-partially reduced graphene oxide nanosheets and a preparation method therefor, wherein the composite material is in the form of a powder, the powder particles thereof comprise the partially reduced graphene oxide nanosheets as a substrate and the trivalent titanium self-doped titanium dioxide nanoparticles as a loading substance, and the trivalent titanium self-doped titanium dioxide nanoparticles are uniformly deposited on the partially reduced graphene oxide nanosheets. The resulting composite material has both an obviously improved photoelectric performance, and also good chemical stability and reusability, the loading of the titanium dioxide nanoparticles on the graphene oxide nanosheets is realized by a one-step hydrothermal method, while realizing the self-doping of the trivalent titanium and the partial reduction of the graphene oxide, the resulting trivalent titanium doped titanium dioxide nanoparticles have a uniform size distribution, and the method thereof has a simple operation, mild conditions and a simple process, which has a good prospect in the fields of photocatalytic degradation of industrial organic dyes and hydrogen production from water by photolysis.

Description

一种三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料及其制备方法Trivalent titanium self-doped titanium dioxide nano particle-partially reduced graphene oxide nanosheet composite material and preparation method thereof 技术领域Technical field
本发明涉及复合材料领域，具体涉及一种三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料的制备方法及制成的复合材料。The invention relates to the field of composite materials, in particular to a preparation method of a trivalent titanium self-doped titanium dioxide nanoparticle-partially reduced graphene oxide nanosheet composite material and a composite material prepared.
背景技术Background technique
环境污染和能源危机是世界面临困扰人类的两大问题，随着社会经济的迅速发展，大量含有有机污染物的工农业废水进入水体，由于这些污染物具有高毒性、难降解及易累积等特点，对生态***和人类健康构成了严重威胁，水中有机污染物的危害引起了世界范围的广泛关注，同样由于耗尽的化石燃料，化石燃料燃烧引起的一系列环境污染问题值得关注，并探索了新的替代清洁能源如氢能是迫切需要的，随着对清洁能源和环保技术迫切需求的日益增长，太阳能的有效应用已经成为许多绿色化学以及电能等具有巨大潜力的应用前景，为了解决一系列的环境及能源问题，多相光催化剂得到众多研究人员重视，可以吸收辐射光，将太阳能转化为电能或化学能，从而有效应用于许多地方，例如有机污染物的光降解，太阳能水分解产氢，染料敏化太阳能电池和二氧化碳光还原，此外，所有这些应用都具有成本低，效率高，使用方便的特点。Environmental pollution and energy crisis are two major problems facing the world. With the rapid development of the social economy, a large number of industrial and agricultural wastewater containing organic pollutants enters the water body. These pollutants are highly toxic, difficult to degrade and easy to accumulate. It poses a serious threat to ecosystems and human health. The harm of organic pollutants in water has caused widespread concern worldwide. Similarly, due to depleted fossil fuels, a series of environmental pollution problems caused by fossil fuel combustion are worthy of attention and explored. New alternative clean energy sources such as hydrogen are urgently needed. With the increasing demand for clean energy and environmental technologies, the effective application of solar energy has become a promising application prospect for many green chemistry and electrical energy, in order to solve a series of problems. Environmental and energy issues, multiphase photocatalysts are valued by many researchers, can absorb radiation, convert solar energy into electrical energy or chemical energy, and thus can be effectively applied to many places, such as photodegradation of organic pollutants, solar water decomposing hydrogen production , dye-sensitized solar cells and Carbon monoxide photoreduction, addition, all of these applications are low cost, high efficiency, easy to use features.
作为新型半导体材料的二氧化钛(TiO 2)被广泛用于有机污染物的光催化降解、气体传感器、染料敏化太阳能电池、生物材料以及光解水产氢，而且其低成本，机械性能好，生物相容性好，与其他半导体光催化材料相比，TiO 2具有生物和化学惰性、氧化能力强、无毒及不易发生光化学腐蚀的优点，已成为光催化剂研究最广泛的研究，不过，以下两个主要缺点大大限制了TiO 2的广泛应用：(1)由于大带隙(锐钛矿为3.2eV，金红石为3.0eV)，其光吸收限制在太阳光谱的UV区域，仅占3-5％的太阳光能；(2)光诱导电荷载体的复合率高。 Titanium dioxide (TiO 2 ), a novel semiconductor material, is widely used for photocatalytic degradation of organic pollutants, gas sensors, dye-sensitized solar cells, biomaterials, and photolysis of hydrogen, and its low cost, good mechanical properties, bio-phase Good compatibility, compared with other semiconductor photocatalytic materials, TiO 2 has the advantages of biological and chemical inertness, strong oxidizing ability, non-toxicity and less prone to photochemical corrosion, and has become the most extensive research on photocatalysts. However, the following two The main disadvantages greatly limit the wide application of TiO 2 : (1) due to the large band gap (3.2 eV for anatase and 3.0 eV for rutile), its light absorption is limited to the UV region of the solar spectrum, accounting for only 3-5%. Solar light energy; (2) The photo-induced charge carrier has a high recombination rate.
针对以上问题，研究人员已经尝试了许多方法，以更有效地将TiO 2从UV响应转移到可见光区域，并降低电子空穴对的重组效率： In response to the above problems, researchers have tried many methods to more efficiently transfer TiO 2 from the UV response to the visible region and reduce the recombination efficiency of electron-hole pairs:
针对第一个问题，为了使TiO 2的光吸收范围扩展到可见光区域，大多数都关注在O或Ti位点引入掺杂剂，以在TiO 2带隙中引入中间隙状态，然而，在TiO 2中引入其他的掺杂剂可能会导致复合材料的热不稳定性，以及增加载流子复合中心，从而影响光电催化的效率，近几年，通过还原TiO 2得到自掺杂Ti 3+的TiO 2(TiO 2-x)，从而达到减少TiO 2带隙能的目的， 已经吸引了国内外研究者的广泛关注，很多已经报道的合成TiO 2-x的方法有化学气相沉积、高能粒子轰击以及高温下真空处理或添加还原剂，但是这些方法操作较复杂，合成条件苛刻以及需要的设施成本高，在工业应用方面会受到一定的影响； In order to solve the first problem, in order to extend the light absorption range of TiO 2 to the visible light region, most of the attention is paid to introducing a dopant at the O or Ti site to introduce a meso gap state in the TiO 2 band gap, however, in TiO The introduction of other dopants in 2 may lead to thermal instability of the composite and increase the carrier recombination center, thereby affecting the efficiency of photoelectrocatalysis. In recent years, self-doping Ti 3+ is obtained by reducing TiO 2 . TiO 2 (TiO 2-x ), which achieves the purpose of reducing the band gap energy of TiO 2 , has attracted wide attention from researchers at home and abroad. Many of the reported methods for synthesizing TiO 2-x include chemical vapor deposition and high-energy particle bombardment. And vacuum treatment or addition of reducing agent at high temperature, but these methods are complicated to operate, the synthesis conditions are harsh and the required facilities are expensive, and will be affected in industrial applications;
针对第二个问题，通常会用一些类似贵金属纳米颗粒或碳基材料的光生电子接收器，由于贵金属成本高昂，不适合大规模应用，因此，低成本的碳基材料可能成为替代稀有贵金属的有效替代品。石墨烯是近年来被发现的一种由碳原子紧密堆积而成的石墨片层并具有蜂窝状结构的二维材料，其特殊的结构使其具有很高的比表面积、优异的导热性能、优异的电子传输能力及较好的吸附性能，非常适合于开发高性能的复合材料。TiO 2与氧化石墨烯(GO)复合后，加快了界面电子传输速率，有效地抑制了光生电子和空穴的复合，提高了对有机物的物理化学吸附，增强了其光催化活性，近年来，众多的研究者广泛使用溶胶-凝胶、原位生长、水热和无氧煅烧等方法来复合TiO 2与氧化石墨烯，应用于光催化降解、水解制氢、太阳能电池、锂离子电池以及抗菌剂等方面，为了提高TiO 2与RGO复合材料的光催化性能，研究者更多的会在复合材料表面进行金属、非金属掺杂，但是这些方法操作较复杂，合成条件苛刻以及需要的设施成本高，在工业应用方面会受到一定的影响。因此，寻找一种更加快速、简单、经济的方法合成TiO 2与RGO复合材料显得尤为重要。因此，针对上述问题，有必要提出进一步的解决方案。 For the second problem, some photo-generated electron receivers like precious metal nanoparticles or carbon-based materials are usually used. Because precious metals are expensive and not suitable for large-scale applications, low-cost carbon-based materials may become effective alternatives to rare precious metals. alternatives. Graphene is a two-dimensional material which has been discovered in recent years and is a graphite sheet which is closely packed with carbon atoms and has a honeycomb structure. Its special structure makes it have a high specific surface area, excellent thermal conductivity and excellent performance. Its electron transport capability and good adsorption performance make it ideal for developing high performance composite materials. When TiO 2 is combined with graphene oxide (GO), the electron transport rate of the interface is accelerated, the recombination of photogenerated electrons and holes is effectively suppressed, the physicochemical adsorption of organic matter is enhanced, and the photocatalytic activity is enhanced. In recent years, Many researchers have used sol-gel, in-situ growth, hydrothermal and anaerobic calcination methods to compound TiO 2 and graphene oxide, which are used in photocatalytic degradation, hydrolyzed hydrogen production, solar cells, lithium ion batteries and antibacterial In order to improve the photocatalytic performance of TiO 2 and RGO composites, researchers will conduct metal and non-metal doping on the surface of composite materials, but these methods are complicated to operate, the synthesis conditions are harsh and the required facility cost. High, will be affected in industrial applications. Therefore, it is particularly important to find a faster, simpler and more economical way to synthesize TiO 2 and RGO composites. Therefore, in order to solve the above problems, it is necessary to propose a further solution.
发明内容Summary of the invention
本发明的目的是：提供一种具有优异的可见光催化性能的三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料。The object of the present invention is to provide a trivalent titanium self-doped titanium dioxide nanoparticle-partially reduced graphene oxide nanosheet composite material having excellent visible light catalytic performance.
为实现上述目的，本发明的技术方案是：一种三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料，所述复合材料呈粉末状，其粉末颗粒包括作为基底的部分还原氧化石墨烯纳米片和作为负载物的三价钛自掺杂二氧化钛纳米颗粒，所述三价钛自掺杂二氧化钛纳米颗粒均匀沉积于所述部分还原氧化石墨烯纳米片上。To achieve the above object, the technical solution of the present invention is: a trivalent titanium self-doped titanium dioxide nanoparticle-partially reduced graphene oxide nanosheet composite material, the composite material being in the form of a powder, the powder particles comprising a portion as a substrate The graphene oxide nanosheet is reduced and the trivalent titanium self-doped titanium dioxide nanoparticle as a support is uniformly deposited on the partially reduced graphene oxide nanosheet.
本发明还提供另外一个技术方案：一种三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料的制备方法，包括如下步骤：The invention also provides another technical solution: a preparation method of a trivalent titanium self-doped titanium dioxide nanoparticle-partially reduced graphene oxide nanosheet composite material, comprising the following steps:
(1)将氧化石墨烯粉末分散于溶剂A中形成混合溶液A；(1) dispersing the graphene oxide powder in the solvent A to form a mixed solution A;
(2)将二氧化钛前驱物分散于溶剂B中形成混合溶液B；(2) dispersing the titanium dioxide precursor in solvent B to form a mixed solution B;
(3)将所述混合溶液B加入到所述混合溶液A中形成混合溶液C；(3) adding the mixed solution B to the mixed solution A to form a mixed solution C;
(4)对所述混合溶液C依次搅拌处理、水热处理以及烘干处理，得到三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料；(4) sequentially performing agitation treatment, hydrothermal treatment, and drying treatment on the mixed solution C to obtain a trivalent titanium self-doped titanium dioxide nanoparticle-partially reduced graphene oxide nanosheet composite material;
其中，所述氧化石墨烯粉末与所述二氧化钛前驱物的质量比为1:5-1:2；Wherein the mass ratio of the graphene oxide powder to the titanium dioxide precursor is 1:5-1:2;
步骤(1)和步骤(2)无先后顺序。Step (1) and step (2) have no order.
上述技术方案中，将石墨通过hummer法转变成氧化石墨烯溶液，再将氧化石墨烯溶液依次通过离心清洗和冻干后获得所述氧化石墨烯粉末。In the above technical solution, the graphite is converted into a graphene oxide solution by a hummer method, and the graphene oxide solution is sequentially obtained by centrifugal washing and lyophilization to obtain the graphene oxide powder.
上述技术方案中，所述氧化石墨烯粉末的质量为0.1g-0.3g，所述二氧化钛前驱物为钛酸四丁酯，所述钛酸四丁酯的体积为0.3ml-0.8ml。In the above technical solution, the graphene oxide powder has a mass of 0.1 g to 0.3 g, the titania precursor is tetrabutyl titanate, and the tetrabutyl titanate has a volume of 0.3 ml to 0.8 ml.
上述技术方案中，所述溶剂A中包括无水乙醇和去离子水，其中的无水乙醇与去离子水的体积比为200:1-250:1，步骤(1)中，首先将所述氧化石墨烯粉末溶于所述无水乙醇中，然后向所述氧化石墨烯粉末和所述无水乙醇形成的溶液中加入所述去离子水，氧化石墨烯粉末与溶剂A的质量比为1:200-1:50。In the above technical solution, the solvent A includes anhydrous ethanol and deionized water, wherein the volume ratio of anhydrous ethanol to deionized water is 200:1-250:1, in the step (1), the first step is The graphene oxide powder is dissolved in the anhydrous ethanol, and then the deionized water is added to the solution of the graphene oxide powder and the anhydrous ethanol, and the mass ratio of the graphene oxide powder to the solvent A is 1. :200-1:50.
上述技术方案中，所述溶剂B为无水乙醇，所述二氧化钛前驱物与所述溶剂B的体积比为1:45-1:40。In the above technical solution, the solvent B is anhydrous ethanol, and the volume ratio of the titanium dioxide precursor to the solvent B is 1:45 to 1:40.
上述技术方案中，步骤(3)中，在不断搅拌所述混合溶液A的同时以滴加的方式将所述混合溶液B加入所述混合溶液A中。In the above technical solution, in the step (3), the mixed solution B is added to the mixed solution A in a dropping manner while continuously stirring the mixed solution A.
上述技术方案中，步骤(4)中的搅拌处理为超声搅拌0.5h-1h。In the above technical solution, the stirring treatment in the step (4) is ultrasonic stirring for 0.5 h to 1 h.
上述技术方案中，步骤(4)中的水热处理的反应温度为200℃-250℃，反应时间为9h-11h。In the above technical solution, the reaction temperature of the hydrothermal treatment in the step (4) is 200 ° C - 250 ° C, and the reaction time is 9 h - 11 h.
上述技术方案中，步骤(4)中的烘干处理为离心烘干。In the above technical solution, the drying treatment in the step (4) is centrifugal drying.
本发明的有益效果是：The beneficial effects of the invention are:
(1)本发明公开的三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料，三价钛的自掺杂使二氧化钛带隙中引入中间隙状态，从而解决了二氧化钛带隙宽的问题，使其光吸收范围扩展到可见光区域，与氧化石墨烯的复合进一步降低了电子与空穴的重组，从而提高复合材料对有机染料的光催化能力以及用于光分解产氢，与单纯的二氧化钛/石墨烯的复合材料相比，掺杂三价钛的二氧化钛/石墨烯复合材料光电性能显著提高，同时具备良好的化学稳定性能和重复利用性，可将发明的三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料应用于光催化降解污染物以及光解水产氢等方面，具备精度高、流程简单、快速经济等优越性；(1) The trivalent titanium self-doped titanium dioxide nanoparticle-partially reduced graphene oxide nanosheet composite material disclosed in the invention, the self-doping of trivalent titanium introduces a gap state in the titanium dioxide band gap, thereby solving the titanium dioxide band gap The wide problem, the light absorption range is extended to the visible light region, and the combination with the graphene oxide further reduces the recombination of electrons and holes, thereby improving the photocatalytic ability of the composite material for the organic dye and the hydrogen decomposition for photolysis, and Compared with the simple titanium dioxide/graphene composite material, the photoelectric properties of the titanium dioxide/graphene composite doped with trivalent titanium are significantly improved, and the chemical stability and recyclability are good, and the trivalent titanium of the invention can be self-doped. The hetero-titanium dioxide nano-particle-reduced graphene oxide nanosheet composite material has the advantages of high precision, simple process, rapid economy and the like in photocatalytic degradation of pollutants and photolysis of hydrogen.
(2)本发明公开的三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料的制备方法，采用一步水热法实现了二氧化钛纳米颗粒在氧化石墨烯纳米片上的负载同时实现了三价钛的自掺杂以及氧化石墨烯的部分还原，获得的三价钛掺杂二氧化钛纳米颗粒尺寸分布均匀，方法操作简单、条件温和、工艺简易，在光催化降解工业有机染料及光解水制氢领域展现出良好的前途。(2) The preparation method of the trivalent titanium self-doped titanium dioxide nanoparticle-partially reduced graphene oxide nanosheet composite material disclosed by the invention realizes the loading of the titanium dioxide nanoparticles on the graphene oxide nanosheet by one-step hydrothermal method The self-doping of trivalent titanium and partial reduction of graphene oxide, the obtained trivalent titanium-doped titanium dioxide nanoparticles have uniform size distribution, the method is simple in operation, mild in condition, simple in process, and photocatalytic degradation of industrial organic dyes and photolysis The field of water hydrogen production shows a good future.
附图说明DRAWINGS
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明中记载的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below. Obviously, the drawings in the following description are only It is a few embodiments described in the present invention, and other drawings can be obtained from those skilled in the art without any inventive effort.
图1为本发明实施例1制备的复合材料的SEM图；1 is an SEM image of a composite material prepared in Example 1 of the present invention;
图2a为本发明实施例1制备的复合材料放大尺寸为50nm的TEM图；2a is a TEM image of a composite material prepared according to Example 1 of the present invention having an enlarged size of 50 nm;
图2b为本发明实施例1制备的复合材料放大尺寸为100nm的TEM图；2b is a TEM image of the composite material prepared in Example 1 of the present invention with an enlarged size of 100 nm;
图2c为本发明实施例1制备的复合材料的SAED图；2c is a SAED diagram of the composite material prepared in Example 1 of the present invention;
图2d为本发明实施例1制备的复合材料体现二氧化钛的晶格间距的HRTEM图；2d is a HRTEM image of the lattice spacing of the composite material prepared in Example 1 of the present invention;
图3a为本发明实施例1制备的复合材料的EDS图；Figure 3a is an EDS diagram of a composite material prepared in Example 1 of the present invention;
图3b为本发明实施例1制备的复合材料的元素分布图谱；Figure 3b is a diagram showing the element distribution of the composite material prepared in Example 1 of the present invention;
图4a为单纯二氧化钛、三价钛自掺杂二氧化钛纳米颗粒以及本发明实施例1制备的复合材料的XPS全谱图；4a is a full spectrum of XPS of a simple titanium dioxide, a trivalent titanium self-doped titanium dioxide nanoparticle, and a composite prepared in Example 1 of the present invention;
图4b为本发明实施例1制备的复合材料对应的Ti元素的XPS窄谱图；4b is an XPS narrow spectrum diagram of Ti element corresponding to the composite material prepared in Example 1 of the present invention;
图4c为本发明实施例1制备的复合材料对应的O元素的XPS窄谱图；4c is an XPS narrow spectrum diagram of the O element corresponding to the composite material prepared in Example 1 of the present invention;
图4d为本发明实施例1制备的复合材料对应的C元素的XPS窄谱图；4d is an XPS narrow spectrum diagram of a C element corresponding to the composite material prepared in Example 1 of the present invention;
图5a为单纯二氧化钛、三价钛自掺杂二氧化钛纳米颗粒以及本发明实施例1制备的复合材料的XRD图谱；5a is an XRD pattern of a simple titanium dioxide, a trivalent titanium self-doped titanium dioxide nanoparticle, and a composite prepared in Example 1 of the present invention;
图5b为单纯二氧化钛、三价钛自掺杂二氧化钛纳米颗粒以及本发明实施例1制备的复合材料的在101面区域的放大XRD图谱；5b is an enlarged XRD pattern of the 101 surface region of the simple titanium dioxide, the trivalent titanium self-doped titanium dioxide nanoparticles, and the composite material prepared in Example 1 of the present invention;
图5c为氧化石墨烯的XRD图谱；Figure 5c is an XRD pattern of graphene oxide;
图6a为单纯二氧化钛、三价钛自掺杂二氧化钛纳米颗粒以及本发明实施例1制备的复合材料的拉曼图谱；6a is a Raman spectrum of a simple titanium dioxide, a trivalent titanium self-doped titanium dioxide nanoparticle, and a composite prepared in Example 1 of the present invention;
图6b为单纯二氧化钛、三价钛自掺杂二氧化钛纳米颗粒以及本发明实施例1制备的复合材料在位移150cm-1处峰的放大拉曼图谱；6b is an enlarged Raman spectrum of a peak of a simple material of titanium dioxide, trivalent titanium self-doped titanium dioxide nanoparticles, and a composite material prepared in Example 1 of the present invention at a displacement of 150 cm-1;
图6c为单纯二氧化钛、三价钛自掺杂二氧化钛纳米颗粒以及本发明实施例1制备的复合材料在D、G峰的放大拉曼图谱；6c is an enlarged Raman spectrum of the D, G peak of the composite material prepared by the simple titanium dioxide, the trivalent titanium self-doped titanium dioxide nanoparticle, and the inventive example 1;
图6d为单纯二氧化钛、氧化石墨烯以及本发明实施例1制备的复合材料的红外图谱；6d is an infrared spectrum of a simple titanium dioxide, graphene oxide, and a composite material prepared in Example 1 of the present invention;
图7a为单纯二氧化钛、三价钛自掺杂二氧化钛纳米颗粒以及本发明实施例1制备的复合材料的紫外-可见光漫反射光谱图；7a is a UV-visible diffuse reflection spectrum of a composite material prepared by using the titanium dioxide, the trivalent titanium self-doped titanium dioxide nanoparticles, and the inventive example 1;
图7b为单纯二氧化钛、三价钛自掺杂二氧化钛纳米颗粒以及本发明实施例1制备的复合材料的光致发光光谱；7b is a photoluminescence spectrum of a simple titanium dioxide, a trivalent titanium self-doped titanium dioxide nanoparticle, and a composite prepared in Example 1 of the present invention;
图7c为单纯二氧化钛、三价钛自掺杂二氧化钛纳米颗粒以及本发明实施例1制备的复合材料的光电流响应图；7c is a photocurrent response diagram of a simple titanium dioxide, a trivalent titanium self-doped titanium dioxide nanoparticle, and a composite prepared in Example 1 of the present invention;
图7d为单纯二氧化钛、三价钛自掺杂二氧化钛纳米颗粒以及本发明实施例1制备的复合材料在光照条件下的阻抗图谱；7d is an impedance spectrum of a simple titanium dioxide, a trivalent titanium self-doped titanium dioxide nanoparticle, and a composite material prepared in Example 1 of the present invention under illumination;
图8a为单纯二氧化钛、三价钛自掺杂二氧化钛纳米颗粒以及本发明实施例1制备的复合材料在可见光条件下降解亚甲基蓝的效率图；8a is a graph showing the efficiency of degrading methylene blue under visible light conditions for a simple titanium dioxide, a trivalent titanium self-doped titanium dioxide nanoparticle, and a composite material prepared in Example 1 of the present invention;
图8b为本发明实施例1制备的复合材料的紫外吸收波长图。Figure 8b is a graph showing the ultraviolet absorption wavelength of the composite material prepared in Example 1 of the present invention.
其中，SEM图：电子扫描显像图；TEM图：透射电子扫描显像图；HRTEM图：高分辨率透射电子扫描显像图；SAED图：选区电子衍射图；EDS图：能谱图；XRD图谱：X射线衍射图谱；XPS谱图：X射线光电子能谱分析谱图。Among them, SEM image: electronic scanning imaging; TEM image: transmission electron scanning imaging; HRTEM image: high-resolution transmission electron scanning imaging; SAED image: selected area electron diffraction pattern; EDS diagram: energy spectrum; XRD Map: X-ray diffraction pattern; XPS spectrum: X-ray photoelectron spectroscopy spectrum.
具体实施方式Detailed ways
为了使本技术领域的人员更好地理解本发明中的技术方案，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都应当属于本发明保护的范围。In order to make those skilled in the art better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. The embodiments are only a part of the embodiments of the invention, and not all of the embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative efforts shall fall within the scope of the present invention.
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合附图和实施例进一步说明本发明的技术方案。但是本发明不限于所列出的实施例，还应包括在本发明所要求的权利范围内其他任何公知的改变。The above described objects, features and advantages of the present invention will become more apparent from the aspects of the appended claims. However, the invention is not limited to the embodiments shown, but also includes any other known changes within the scope of the claims.
首先，此处所称的“一个实施例”或“实施例”是指可包含于本发明至少一个实现方式中的特定特征、结构或特性。在本说明书中不同地方出现的“在一个实施例中”并非均指同一个实施例，也不是单独的或选择性的与其他实施例互相排斥的实施例。First, "an embodiment" or "an embodiment" as used herein refers to a particular feature, structure, or characteristic that can be included in at least one implementation of the invention. The appearances of the "in one embodiment", "a" or "an"
其次，本发明利用结构示意图等进行详细描述，在详述本发明实施例时，为便于说明，示意图会不依一般比例作局部放大，而且所述示意图只是实例，其在此不应限制本发明保护的范围。The present invention will be described in detail with reference to the accompanying drawings and the like. The scope.
实施例1Example 1
一、以下为三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料的制备方法：First, the following is a preparation method of trivalent titanium self-doped titanium dioxide nanoparticles-partially reduced graphene oxide nanosheet composite material:
将合成的氧化石墨烯水溶液离心清洗后冻干得到可溶于无水乙醇的干燥的氧化石墨烯粉 末，将0.1g氧化石墨烯粉末分散于20ml无水乙醇中，然后加入0.1ml去离子水形成混合溶液A，将0.3ml二氧化钛前驱物钛酸四丁酯与20ml无水乙醇形成混合溶液B，将混合溶液B缓慢滴加到混合溶液A中形成混合溶液C，将混合溶液C超声搅拌1h，然后将混合溶液C在220℃的反应温度下反应10h，之后离心烘干，得到三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料。The synthesized graphene oxide aqueous solution is centrifuged and then freeze-dried to obtain dried graphene oxide powder soluble in absolute ethanol, 0.1 g of graphene oxide powder is dispersed in 20 ml of absolute ethanol, and then 0.1 ml of deionized water is added to form Mixing solution A, 0.3 ml of titanium dioxide precursor tetrabutyl titanate and 20 ml of absolute ethanol are mixed to form a mixed solution B, and the mixed solution B is slowly added dropwise to the mixed solution A to form a mixed solution C, and the mixed solution C is ultrasonically stirred for 1 hour. Then, the mixed solution C was reacted at a reaction temperature of 220 ° C for 10 hours, and then centrifugally dried to obtain a trivalent titanium self-doped titanium oxide nanoparticle-partially reduced graphene oxide nanosheet composite material.
上述氧化石墨烯粉末采用如下方法制成：合成氧化石墨烯，冰浴15℃以下，将2g石墨和6g高锰酸钾溶于46mL无水浓硫酸中，升温至35℃并搅拌2h，升温至80℃滴加100ml水，然后升温至95℃加300ml水，滴加无水双氧水1-2ml，处理条件：冻干。The above graphene oxide powder is prepared by synthesizing graphene oxide in an ice bath at 15 ° C or less, dissolving 2 g of graphite and 6 g of potassium permanganate in 46 mL of anhydrous concentrated sulfuric acid, raising the temperature to 35 ° C and stirring for 2 h, and heating up to 100 ml of water was added dropwise at 80 ° C, then the temperature was raised to 95 ° C and 300 ml of water, and 1-2 ml of anhydrous hydrogen peroxide was added dropwise. The treatment conditions were lyophilized.
二、以下为对制备好的三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料作光电测试的过程：Second, the following is the photoelectric test of the prepared trivalent titanium self-doped titanium dioxide nanoparticle-partially reduced graphene oxide nanosheet composite material:
分别制作工作电极、配置支持电解液、准备对电极和参比电极，①制作工将5mg三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料的粉末溶于500uL异丙醇中，再滴加50uL的0.5％的全氟磺酸型聚合物溶液，超声处理1h，得到复合材料混合溶液，取3uL上述复合材料混合溶液滴加在玻碳电极上，作为工作电极；②配置0.1M亚硫酸钠做支持电解液；③使用铂丝作对电极；④甘汞电极作参比电极；利用电化学工作站的计时电位法检测复合材料的光电流效应，其中有无光照的时间间隔为30s。Prepare the working electrode, configure the supporting electrolyte, prepare the counter electrode and the reference electrode separately. 1 The manufacturer dissolves the powder of 5 mg of trivalent titanium self-doped titanium dioxide nanoparticles-partially reduced graphene oxide nanosheet composite into 500 uL of isopropanol. 50uL of 0.5% perfluorosulfonic acid type polymer solution was added dropwise, sonicated for 1h to obtain a composite material mixed solution, and 3uL of the above composite material mixed solution was added to the glassy carbon electrode as a working electrode; 0.1M sodium sulfite was used as the supporting electrolyte; 3 was used as the counter electrode; 4 calomel electrode was used as the reference electrode; the photocurrent effect of the composite was detected by the chronopotentiometry of the electrochemical workstation, and the time interval with or without illumination was 30 s.
三、以下为对制备好的三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料作光催化降解有机污染废水过程：3. The following is a photocatalytic process for the degradation of organic contaminated wastewater by the prepared trivalent titanium self-doped titanium dioxide nanoparticle-partially reduced graphene oxide nanosheet composite material:
将单纯二氧化钛、三价钛自掺杂二氧化钛纳米颗粒以及制备的复合材料分别浸渍于初始浓度为40mg/L的亚甲基蓝污染水溶液中，先在黑暗环境中搅拌12小时达到吸附平衡状态后，再在可见光下照射0-120min，时间间隔为30min，每个时间间隔，取对应溶液测试紫外可见光光谱吸收值。The titanium dioxide, the trivalent titanium self-doped titanium dioxide nanoparticles and the prepared composite material were respectively immersed in a methylene blue contaminated aqueous solution having an initial concentration of 40 mg/L, and stirred in a dark environment for 12 hours to reach an adsorption equilibrium state, and then in visible light. The lower irradiation was 0-120 min, and the time interval was 30 min. At each time interval, the corresponding solution was used to test the ultraviolet-visible absorption value.
四、以下为对制备的复合材料进行检测和实验的结果：4. The following are the results of testing and testing the prepared composite materials:
(一)图1为制备的复合材料的SEM图，可以看见二氧化钛纳米颗粒均匀沉积在石墨烯纳米片的表面；(A) Figure 1 is an SEM image of the prepared composite material, it can be seen that the titanium dioxide nanoparticles are uniformly deposited on the surface of the graphene nanosheet;
(二)图2a为制备的复合材料放大尺寸为50nm的TEM图，图2b为制备的复合材料放大尺寸为100nm的TEM图，进一步证明了三价钛自掺杂二氧化钛纳米颗粒均匀沉积在石墨烯纳米片的表面，三价钛自掺杂二氧化钛纳米颗粒尺寸大约为6nm；(2) Figure 2a shows the TEM image of the composite material with a magnification of 50 nm, and Figure 2b shows the TEM image of the composite material with a magnification of 100 nm, which further proves that the trivalent titanium self-doped titanium dioxide nanoparticles are uniformly deposited on the graphene. The surface of the nanosheet, the size of the trivalent titanium self-doped titanium dioxide nanoparticles is about 6 nm;
图2c为制备的复合材料的SAED图，图2d为制备的复合材料体现二氧化钛的晶格间距的HRTEM图，TiO 2锐钛矿型(101)晶面晶格间距为0.35nm； 2c is a SAED diagram of the prepared composite material, and FIG. 2d is a HRTEM image of the lattice spacing of the prepared composite material exhibiting titanium dioxide, and the TiO 2 anatase type (101) crystal plane lattice spacing is 0.35 nm;
(三)图3a为制备的复合材料的EDS图，图3b为制备的复合材料的元素分布图谱，表 明金修饰钼酸铋纳米片/二氧化钛纳米管阵列主要含有Ti、O、C三种元素；(3) Figure 3a is an EDS diagram of the prepared composite material, and Figure 3b is an elemental distribution map of the prepared composite material, indicating that the gold-modified bismuth molybdate nanosheet/titanium dioxide nanotube array mainly contains three elements of Ti, O, and C;
(四)图4a为单纯二氧化钛、三价钛自掺杂二氧化钛纳米颗粒以及制备的复合材料的XPS全谱图，图4b为制备的复合材料对应的Ti元素的XPS窄谱图；图4c为制备的复合材料对应的O元素的XPS窄谱图，图4d为制备的复合材料对应的C元素的XPS窄谱图，图4a全谱中可以明显看到有Ti、O、C三种元素的峰，从Ti 2p高分辨XPS窄谱中可以明显看出三价钛的峰，从样品的C 1s高分辨XPS窄谱可以看出C＝O基本消失，表明GO中的含氧官能团在水热反应过程中被部分还原，可见水热反应使得三价钛掺杂和石墨烯还原同时进行；(4) Figure 4a shows the XPS full spectrum of the simple titanium dioxide, trivalent titanium self-doped titanium dioxide nanoparticles and the prepared composite material, and Figure 4b shows the XPS narrow spectrum of the Ti element corresponding to the prepared composite material; Figure 4c shows the preparation The composite material corresponds to the XPS narrow spectrum of the O element, and Figure 4d shows the XPS narrow spectrum of the C element corresponding to the composite. The peaks of the Ti, O and C elements can be clearly seen in the full spectrum of Figure 4a. From the Ti 2p high-resolution XPS narrow spectrum, the peak of trivalent titanium can be clearly seen. From the C 1s high-resolution XPS narrow spectrum of the sample, it can be seen that C=O disappears, indicating that the oxygen-containing functional group in GO is hydrothermally reacted. Partially reduced in the process, it can be seen that the hydrothermal reaction causes the trivalent titanium doping and graphene reduction to proceed simultaneously;
(五)图5a为单纯二氧化钛、三价钛自掺杂二氧化钛纳米颗粒以及制备的复合材料的XRD图谱，图5b为单纯二氧化钛、三价钛自掺杂二氧化钛纳米颗粒以及制备的复合材料的在101面区域的放大XRD图谱，图5c为氧化石墨烯的XRD图谱，可以看出三价钛自掺杂二氧化钛纳米颗粒和制备的复合材料相对单纯的二氧化钛的XRD峰向左偏移，这种现象归因于三价钛自掺杂二氧化钛纳米颗粒以及制备的复合材料样品中存在三价钛掺杂；图5c图中没有出现氧化石墨稀的特征衍射峰,出现了对应于二氧化钛的衍射峰,这可能是由于超声分散和随后的水热处理对氧化石墨烯的有序层状结构造成破坏,形成了部分还原的氧化石墨烯,且二氧化钛晶粒在氧化石墨烯片层表面形成,阻碍了氧化石墨烯层片的有序堆积，与图2c的结果相吻合)(5) Figure 5a shows the XRD pattern of the pure titanium dioxide, trivalent titanium self-doped titanium dioxide nanoparticles and the prepared composite material, and Figure 5b shows the simple titanium dioxide, trivalent titanium self-doped titanium dioxide nanoparticles and the prepared composite material in 101 The enlarged XRD pattern of the surface region, Figure 5c is the XRD pattern of graphene oxide. It can be seen that the XRD peak of the trivalent titanium self-doped titanium dioxide nanoparticles and the prepared composite material is shifted to the left relative to the XRD peak of the simple titanium dioxide. Due to the presence of trivalent titanium self-doped titanium dioxide nanoparticles and the prepared composite samples, there is trivalent titanium doping; in Figure 5c, there is no characteristic diffraction peak of graphite oxide thin, and a diffraction peak corresponding to titanium dioxide appears, which may It is due to the ultrasonic dispersion and subsequent hydrothermal treatment to destroy the ordered layered structure of graphene oxide, forming partially reduced graphene oxide, and the titanium dioxide grains are formed on the surface of the graphene oxide sheet, which hinders the graphene oxide layer. Ordered accumulation of slices, consistent with the results of Figure 2c)
(六)图6a为单纯二氧化钛、三价钛自掺杂二氧化钛纳米颗粒以及制备的复合材料的拉曼图谱，图6a中未经修饰的二氧化钛表现出典型的锐钛矿型拉曼光谱，而自掺杂Ti 3+的二氧化钛晶体出现了新的峰位，说明还原Ti 3+之后二氧化钛结构发生变化导致了无序，从而激发晶体的边缘区； (6) Figure 6a shows the Raman spectrum of pure titanium dioxide, trivalent titanium self-doped titanium dioxide nanoparticles and the prepared composite. The unmodified titanium dioxide in Figure 6a shows a typical anatase Raman spectrum. A new peak position appears in the Ti 3+ doped titanium dioxide crystal, indicating that the change of the titanium dioxide structure after the reduction of Ti 3+ leads to disorder, thereby exciting the edge region of the crystal;
图6b为单纯二氧化钛、三价钛自掺杂二氧化钛纳米颗粒以及制备的复合材料在位移150cm -1处峰的放大拉曼图谱，图6c为单纯二氧化钛、三价钛自掺杂二氧化钛纳米颗粒以及制备的复合材料在D、G峰的放大拉曼图谱，可明显看出三价钛自掺杂二氧化钛纳米颗粒以及三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料的峰向高的位移方向偏移，说明复合材料中有三价钛掺杂，从图6c中看出，D峰要大于G峰，说明部分氧化石墨烯还原得到部分还原氧化石墨烯，可见水热反应使得三价钛掺杂和石墨烯还原同时进行，该证明同时符合XPS以及XRD的结果分析； Figure 6b is an enlarged Raman spectrum of a simple titanium dioxide, trivalent titanium self-doped titanium dioxide nanoparticle and a prepared composite at a displacement of 150 cm -1 , and Figure 6c is a simple titanium dioxide, trivalent titanium self - doped titanium dioxide nanoparticle and preparation thereof The magnified Raman spectra of the composites at D and G peaks clearly show the peak directions of trivalent titanium self-doped titanium dioxide nanoparticles and trivalent titanium self-doped titanium dioxide nanoparticles-partially reduced graphene oxide nanosheet composites. The high displacement direction shift indicates that there is trivalent titanium doping in the composite. As shown in Fig. 6c, the D peak is larger than the G peak, indicating that partial oxidation of graphene is reduced to obtain partially reduced graphene oxide, which shows that the hydrothermal reaction makes three The valence titanium doping and graphene reduction are carried out simultaneously, and the proof conforms to the results of XPS and XRD analysis;
图6d为单纯二氧化钛、氧化石墨烯以及制备的复合材料的红外图谱，氧化石墨烯的片层上含有很多含氧官能团，3403cm -1处出现的宽吸收峰对应的是－OH的伸缩振动吸收峰，1728cm -1归属于C＝O的伸缩振动，1626cm -1是未被氧化的石墨区的骨架振动峰，伸缩振动 峰，1072cm -1是C－O－C中C－O的伸缩振动峰，从三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料复合物的红外光谱图可以看出，复合物中氧化石墨烯的主要含氧官能团的振动峰，如1728cm -1、1390cm -1、1238cm -1和1072cm -1的强度都有明显的减弱，说明氧化石墨烯在水热过程中发生了一定程度的还原，但并没有完全还原为石墨烯。479cm -1处出现的强吸收峰归属于Ti－O－Ti的伸缩振动，说明二氧化钛和氧化石墨烯更好的进行了结合； Figure 6d shows the infrared spectrum of simple titanium dioxide, graphene oxide and the prepared composite. The graphene oxide layer contains many oxygen-containing functional groups, and the broad absorption peak appearing at 3403 cm -1 corresponds to the stretching vibration absorption peak of -OH. 1728 cm -1 is a stretching vibration attributed to C=O, and 1626 cm -1 is a skeleton vibration peak of an unoxidized graphite region, and a stretching vibration peak, 1072 cm -1 is a stretching vibration peak of C-O in C-O-C, From the infrared spectrum of the trivalent titanium self-doped titanium dioxide nanoparticle-partially reduced graphene oxide nanosheet composite composite, it can be seen that the vibration peak of the main oxygen-containing functional group of graphene oxide in the composite, such as 1728 cm -1 , The strengths of 1390cm -1 , 1238cm -1 and 1072cm -1 are obviously weakened, indicating that graphene oxide has a certain degree of reduction during hydrothermal process, but it has not been completely reduced to graphene. The strong absorption peak appearing at 479 cm -1 is attributed to the stretching vibration of Ti-O-Ti, indicating that titanium dioxide and graphene oxide are better combined;
(七)图7a为单纯二氧化钛、三价钛自掺杂二氧化钛纳米颗粒以及制备的复合材料的紫外-可见光漫反射光谱图，其反映了所制备的光催化剂的光学性质和不同的带隙结构，单纯二氧化钛只吸收紫外光，其基本吸收边缘接近400nm，与单纯二氧化钛相比，三价钛自掺杂二氧化钛纳米颗粒和三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料在400和800nm之间区域的吸收进一步提高；(7) Figure 7a shows the UV-visible diffuse reflectance spectra of pure titanium dioxide, trivalent titanium self-doped titanium dioxide nanoparticles and composites prepared, which reflect the optical properties and different band gap structures of the prepared photocatalysts. Titanium dioxide alone absorbs only ultraviolet light, and its basic absorption edge is close to 400 nm. Compared with titanium dioxide alone, trivalent titanium self-doped titanium dioxide nanoparticles and trivalent titanium self-doped titanium dioxide nanoparticles-partially reduced graphene oxide nanosheet composites The absorption in the region between 400 and 800 nm is further increased;
图7b为单纯二氧化钛、三价钛自掺杂二氧化钛纳米颗粒以及制备的复合材料的光致发光光谱，单纯的二氧化钛呈现较高的发射峰强度，三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料的PL强度进一步减弱，说明界面电子从三价钛自掺杂二氧化钛的导带转移到部分还原氧化石墨烯纳米片表面，降低了电子和空穴的重组，从而增强了三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料的光催化活性；Figure 7b shows the photoluminescence spectra of simple titanium dioxide, trivalent titanium self-doped titanium dioxide nanoparticles and composites prepared. The simple titanium dioxide exhibits a high emission peak intensity, and the trivalent titanium self-doped titanium dioxide nanoparticles - partial reduction oxidation The PL strength of graphene nanosheet composites is further weakened, indicating that the interface electrons are transferred from the conduction band of trivalent titanium self-doped titanium dioxide to the surface of partially reduced graphene oxide nanosheets, which reduces the recombination of electrons and holes, thereby enhancing the three Photocatalytic activity of valence titanium self-doped titanium dioxide nanoparticles-partially reduced graphene oxide nanosheet composites;
图7c为单纯二氧化钛、三价钛自掺杂二氧化钛纳米颗粒以及制备的复合材料的光电流响应图，以0.1M的无水硫酸钠为电解液，氙灯(用滤光片滤掉400nm以下的波长)模拟可见光，光源到烧杯的距离为15cm，光照强度为60mW/cm 2，在CHI660D电化学工作站三电极体系下进行光电流测试，三价钛自掺杂二氧化钛纳米颗粒以及三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料的光电流密度分别为0.0025、0.0046、0.0192、0.0132mA/cm 2，分别是单纯二氧化钛的光电流密度(0.0006mA/cm 2)的4倍、7.7倍、32倍、22倍，表示TiO 2纳米管阵列修饰钼酸铋纳米片和金纳米颗粒后提高了电子空穴对的分离效率，可以看出当氧化石墨烯用量增加到0.2g时光电流密度最高，继续增加氧化石墨烯量，光电流密度呈下降趋势； Fig. 7c is a photocurrent response diagram of a simple titanium dioxide, a trivalent titanium self-doped titanium dioxide nanoparticle, and a composite material prepared by using a 0.1 M anhydrous sodium sulfate as an electrolyte, and filtering a wavelength below 400 nm with a filter. Simulated visible light, the distance from the light source to the beaker is 15cm, the light intensity is 60mW/cm 2 , the photocurrent test is carried out under the three-electrode system of the CHI660D electrochemical workstation, the trivalent titanium self-doped titanium dioxide nanoparticles and the trivalent titanium self-doping The photocurrent densities of the titanium dioxide nanoparticle-partially reduced graphene oxide nanosheet composites are 0.0025, 0.0046, 0.0192, and 0.0132 mA/cm 2 , respectively, which are four times the photocurrent density (0.0006 mA/cm 2 ) of the simple titanium dioxide. 7.7 times, 32 times, 22 times, indicating that the TiO 2 nanotube array modified bismuth molybdate nanosheets and gold nanoparticles improved the separation efficiency of electron-hole pairs. It can be seen that the photocurrent when the amount of graphene oxide is increased to 0.2g The highest density, continue to increase the amount of graphene oxide, the photocurrent density shows a downward trend;
图7d为单纯二氧化钛、三价钛自掺杂二氧化钛纳米颗粒以及制备的复合材料在光照条件下的阻抗图谱，以0.1M的无水硫酸钠为电解液，氙灯(用滤光片滤掉400nm以下的波长)模拟可见光，光源到烧杯的距离为15cm，光照强度为60mW/cm2，在CHI660D电化学工作站三电极体系下进行交流阻抗测试。在光照条件下，单纯二氧化钛、三价钛自掺杂二氧化钛纳米颗粒以及三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料的交流阻抗图谱。与单纯二氧化钛相比较，三价钛自掺杂二氧化钛纳米颗粒显示较小的半圆形，表 明在三价钛自掺杂二氧化钛电极上实现了有效的光生电子-空穴分离。此外，三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料显示了交流阻抗光谱中最小的半圆弧，表明在引入石墨烯后，电子受体发生更快的界面电荷转移并导致电子-空穴对的有效分离；Figure 7d shows the impedance spectrum of pure titanium dioxide, trivalent titanium self-doped titanium dioxide nanoparticles and the prepared composite under light conditions. The 0.1M anhydrous sodium sulfate is used as the electrolyte, and the xenon lamp is filtered by filters below 400 nm. The wavelength is simulated by visible light. The distance from the light source to the beaker is 15 cm, and the light intensity is 60 mW/cm2. The AC impedance test is performed under the three-electrode system of the CHI660D electrochemical workstation. Under light conditions, the AC impedance spectra of pure titanium dioxide, trivalent titanium self-doped titanium dioxide nanoparticles and trivalent titanium self-doped titanium dioxide nanoparticles-partially reduced graphene oxide nanosheet composites. Compared with simple titanium dioxide, the trivalent titanium self-doped titanium dioxide nanoparticles show a smaller semicircle, indicating that effective photogenerated electron-hole separation is achieved on the trivalent titanium self-doped titanium dioxide electrode. In addition, the trivalent titanium self-doped titanium dioxide nanoparticle-partially reduced graphene oxide nanosheet composite shows the smallest semi-circular arc in the AC impedance spectrum, indicating that the electron acceptor undergoes faster interfacial charge transfer after the introduction of graphene. And lead to efficient separation of electron-hole pairs;
图8a为单纯二氧化钛、三价钛自掺杂二氧化钛纳米颗粒以及制备的复合材料在可见光条件下降解亚甲基蓝的效率图，图8b为制备的复合材料的紫外吸收波长图。Fig. 8a is a graph showing the efficiency of degrading methylene blue under visible light conditions by simple titanium dioxide, trivalent titanium self-doped titanium dioxide nanoparticles and the prepared composite material, and Fig. 8b is a UV absorption wavelength diagram of the prepared composite material.
用500W氙灯光照单纯二氧化钛、三价钛自掺杂二氧化钛纳米颗粒以及三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料在可见光下降解亚甲基蓝，与单纯二氧化钛相比较，三价钛自掺杂二氧化钛对亚甲基蓝的降解效率明显提高，同时三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料对亚甲基蓝的光降解在120min时基本降解完全，降解效率达到100％。Using 500W xenon lamp to illuminate simple titanium dioxide, trivalent titanium self-doped titanium dioxide nanoparticles and trivalent titanium self-doped titanium dioxide nanoparticles-partially reduced graphene oxide nanosheet composites to degrade methylene blue under visible light, compared with simple titanium dioxide, trivalent The degradation efficiency of methylene blue by titanium self-doped titanium dioxide is obviously improved. At the same time, the photodegradation of methylene blue by trivalent titanium self-doped titanium dioxide nanoparticles-partially reduced graphene oxide nanosheet composites is basically degraded at 120 min, and the degradation efficiency reaches 100%. .
实施例2Example 2
以下为三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料的制备方法：将合成的氧化石墨烯水溶液经离心清洗后冻干得到可溶于无水乙醇的干燥的氧化石墨烯粉末，将0.2g氧化石墨烯粉末分散于20ml无水乙醇中，再加入0.1ml去离子水形成混合溶液A，将0.5ml二氧化钛前驱物钛酸四丁酯与20ml无水乙醇形成混合溶液B，将混合溶液B混合溶液缓慢滴加到混合溶液A中形成混合溶液C，将混合溶液C超声搅拌1h后，然后将混合溶液C在220℃的反应温度下反应10h，之后离心烘干，得到三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料。The following is a preparation method of trivalent titanium self-doped titanium dioxide nanoparticle-partially reduced graphene oxide nanosheet composite material: the synthesized graphene oxide aqueous solution is centrifugally washed and freeze-dried to obtain dried graphite oxide soluble in absolute ethanol. The olefin powder, 0.2 g of graphene oxide powder is dispersed in 20 ml of absolute ethanol, 0.1 ml of deionized water is further added to form a mixed solution A, and 0.5 ml of a titanium dioxide precursor tetrabutyl titanate is formed into a mixed solution with 20 ml of absolute ethanol. The mixed solution B mixed solution was slowly added dropwise to the mixed solution A to form a mixed solution C, and the mixed solution C was ultrasonically stirred for 1 hour, and then the mixed solution C was reacted at a reaction temperature of 220 ° C for 10 hours, followed by centrifugation and drying to obtain Trivalent titanium self-doped titanium dioxide nanoparticles-partially reduced graphene oxide nanosheet composite.
对本实施例制备的复合材料的光电测试过程和光催化降解有机污染废水过程参考实施例1。The photoelectric test process of the composite material prepared in the present embodiment and the photocatalytic degradation process of the organic pollution wastewater are referred to in Reference Example 1.
实施例3Example 3
以下为三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料的制备方法：将合成的氧化石墨烯水溶液经离心清洗后冻干得到可溶于无水乙醇的干燥的氧化石墨烯，将0.3g氧化石墨烯粉末分散于20ml无水乙醇中，然后加入0.1ml去离子水形成混合溶液A，将0.8ml二氧化钛前驱物钛酸四丁酯与20ml无水乙醇形成混合溶液B，将混合溶液B缓慢滴加到混合溶液A中形成混合溶液C，将混合溶液C超声搅拌1h，然后将混合溶液C在反应温度为220℃的条件下水热反应10h，然后离心烘干，得到三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料。The following is a preparation method of trivalent titanium self-doped titanium dioxide nanoparticle-partially reduced graphene oxide nanosheet composite material: the synthesized graphene oxide aqueous solution is centrifugally washed and freeze-dried to obtain dried graphite oxide soluble in absolute ethanol. Alkenes, 0.3 g of graphene oxide powder was dispersed in 20 ml of absolute ethanol, then 0.1 ml of deionized water was added to form a mixed solution A, and 0.8 ml of a titanium dioxide precursor tetrabutyl titanate and 20 ml of absolute ethanol were mixed to form a mixed solution B. The mixed solution B was slowly added dropwise to the mixed solution A to form a mixed solution C, and the mixed solution C was ultrasonically stirred for 1 h, and then the mixed solution C was hydrothermally reacted at a reaction temperature of 220 ° C for 10 h, and then centrifuged to obtain three Titanium self-doped titanium dioxide nanoparticles-partially reduced graphene oxide nanosheet composites.
对本实施例制备的复合材料的光电测试过程和光催化降解有机污染废水过程参考实施例1。The photoelectric test process of the composite material prepared in the present embodiment and the photocatalytic degradation process of the organic pollution wastewater are referred to in Reference Example 1.
当然上述实施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。凡根据本发明主要技术方案的精神实质所做的修饰，都应涵盖在本发明的保护范围之内。The embodiments described above 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. Modifications made in accordance with the spirit of the main technical solutions of the present invention are intended to be included within the scope of the present invention.

Claims (10)

  1. 一种三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料，其特征在于，所述复合材料呈粉末状，其粉末颗粒包括作为基底的部分还原氧化石墨烯纳米片和作为负载物的三价钛自掺杂二氧化钛纳米颗粒，所述三价钛自掺杂二氧化钛纳米颗粒均匀沉积于所述部分还原氧化石墨烯纳米片上。A trivalent titanium self-doped titanium dioxide nanoparticle-partially reduced graphene oxide nanosheet composite material, characterized in that the composite material is in the form of a powder, and the powder particles thereof comprise a partially reduced graphene oxide nanosheet as a substrate and The trivalent titanium of the load is self-doped with titanium dioxide nanoparticles, and the trivalent titanium self-doped titanium dioxide nanoparticles are uniformly deposited on the partially reduced graphene oxide nanosheet.
  2. 一种三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料的制备方法，其特征在于，包括如下步骤：A method for preparing a trivalent titanium self-doped titanium dioxide nanoparticle-partially reduced graphene oxide nanosheet composite material, comprising the steps of:
    (1)将氧化石墨烯粉末分散于溶剂A中形成混合溶液A；(1) dispersing the graphene oxide powder in the solvent A to form a mixed solution A;
    (2)将二氧化钛前驱物分散于溶剂B中形成混合溶液B；(2) dispersing the titanium dioxide precursor in solvent B to form a mixed solution B;
    (3)将所述混合溶液B加入到所述混合溶液A中形成混合溶液C；(3) adding the mixed solution B to the mixed solution A to form a mixed solution C;
    (4)对所述混合溶液C依次搅拌处理、水热处理以及烘干处理，得到三价钛自掺杂二氧化钛纳米颗粒-部分还原氧化石墨烯纳米片复合材料；(4) sequentially performing agitation treatment, hydrothermal treatment, and drying treatment on the mixed solution C to obtain a trivalent titanium self-doped titanium dioxide nanoparticle-partially reduced graphene oxide nanosheet composite material;
    其中，所述氧化石墨烯粉末与所述二氧化钛前驱物的质量比为1:5-1:2；Wherein the mass ratio of the graphene oxide powder to the titanium dioxide precursor is 1:5-1:2;
    步骤(1)和步骤(2)无先后顺序。Step (1) and step (2) have no order.
  3. 根据权利要求2所述的制备方法，其特征在于，将石墨通过hummer法转变成氧化石墨烯溶液，再将氧化石墨烯溶液依次通过离心清洗和冻干后获得所述氧化石墨烯粉末。The preparation method according to claim 2, wherein the graphite is converted into a graphene oxide solution by a hummer method, and the graphene oxide solution is sequentially subjected to centrifugal washing and lyophilization to obtain the graphene oxide powder.
  4. 根据权利要求2所述的制备方法，其特征在于，所述氧化石墨烯粉末的质量为0.1g-0.3g，所述二氧化钛前驱物为钛酸四丁酯，所述钛酸四丁酯的体积为0.3ml-0.8ml。The preparation method according to claim 2, wherein the graphene oxide powder has a mass of 0.1 g to 0.3 g, the titania precursor is tetrabutyl titanate, and the tetrabutyl titanate has a volume. It is from 0.3ml to 0.8ml.
  5. 根据权利要求2所述的制备方法，其特征在于，所述溶剂A中包括无水乙醇和去离子水，其中的无水乙醇与去离子水的体积比为200:1-250:1，步骤(1)中，首先将所述氧化石墨烯粉末溶于所述无水乙醇中，然后向所述氧化石墨烯粉末和所述无水乙醇形成的溶液中加入所述去离子水，氧化石墨烯粉末与溶剂A的质量比为1:200-1:50。The preparation method according to claim 2, wherein the solvent A comprises anhydrous ethanol and deionized water, wherein the volume ratio of anhydrous ethanol to deionized water is 200:1-250:1, the step (1) First, the graphene oxide powder is dissolved in the anhydrous ethanol, and then the deionized water, graphene oxide is added to a solution of the graphene oxide powder and the anhydrous ethanol. The mass ratio of the powder to the solvent A is 1:200 to 1:50.
  6. 根据权利要求2所述的制备方法，其特征在于，所述溶剂B为无水乙醇，所述二氧化钛前驱物与所述溶剂B的体积比为1:45-1:40。The preparation method according to claim 2, wherein the solvent B is absolute ethanol, and the volume ratio of the titanium dioxide precursor to the solvent B is 1:45 to 1:40.
  7. 根据权利要求2所述的制备方法，其特征在于，步骤(3)中，在不断搅拌所述混合溶液A的同时以滴加的方式将所述混合溶液B加入所述混合溶液A中。The production method according to claim 2, wherein in the step (3), the mixed solution B is added to the mixed solution A in a dropping manner while continuously stirring the mixed solution A.
  8. 根据权利要求2所述的制备方法，其特征在于，步骤(4)中的搅拌处理为超声搅拌0.5h-1h。The preparation method according to claim 2, wherein the stirring treatment in the step (4) is ultrasonic stirring for 0.5 h to 1 h.
  9. 根据权利要求2所述的制备方法，其特征在于，步骤(4)中的水热处理的反应温度为200℃-250℃，反应时间为9h-11h。The preparation method according to claim 2, wherein the reaction temperature of the hydrothermal treatment in the step (4) is from 200 ° C to 250 ° C, and the reaction time is from 9 h to 11 h.
  10. 根据权利要求2所述的制备方法，其特征在于，步骤(4)中的烘干处理为离心烘干。The preparation method according to claim 2, wherein the drying treatment in the step (4) is centrifugal drying.
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