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Graphene quantum dot modified manganese oxide/titanium oxide nanotube array material and preparation method and application thereof

A technology of titanium oxide nanotubes and graphene quantum dots, applied in metal/metal oxide/metal hydroxide catalysts, chemical instruments and methods, chemical/physical processes, etc., can solve the problem of low photocatalytic efficiency and visible light utilization. Low, photogenerated electron-hole recombination rate is high

Inactive Publication Date: 2019-05-24
HEFEI UNIV OF TECH
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Problems solved by technology

However, TiO 2 As a photocatalyst, there are two key problems. First, TiO 2 The forbidden band width Eg=3.2eV, the band gap is wide, and can only absorb photons with a wavelength less than 378nm, and the utilization rate of light, especially visible light, is very low; secondly, the recombination rate of photogenerated electrons-holes is very high, which leads to its The photocatalytic efficiency in the actual reaction is low
These two defects severely limit its practical application

Method used

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  • Graphene quantum dot modified manganese oxide/titanium oxide nanotube array material and preparation method and application thereof
  • Graphene quantum dot modified manganese oxide/titanium oxide nanotube array material and preparation method and application thereof
  • Graphene quantum dot modified manganese oxide/titanium oxide nanotube array material and preparation method and application thereof

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preparation example Construction

[0026] The invention provides a method for preparing a graphene quantum dot modified manganese oxide / titanium oxide nanotube array material, comprising the following steps:

[0027] Using titanium sheet as the positive electrode and graphite plate as the negative electrode, anodic oxidation and annealing are performed sequentially to obtain titanium oxide nanotube arrays in the anatase phase;

[0028] Preoxidizing the reduced graphene oxide in concentrated sulfuric acid and concentrated nitric acid solutions to obtain preoxidized graphene;

[0029] After mixing the pre-oxidized graphene and water, the ammonia water adjusts the pH value to be weakly alkaline, and performs a hydrothermal reaction to obtain a graphene quantum dot solution;

[0030] Taking the titanium oxide nanotube array in the anatase phase as the positive electrode, and the platinum sheet as the negative electrode, immersing in the graphene quantum dot solution, and performing an electrolytic reaction to obtai...

Embodiment 1

[0052] First, cut the titanium sheet into a 2*4cm sheet, place it in acetone, ethanol, and deionized water for 15 minutes, and then place it in ethylene glycol electrolysis containing 0.25mol ammonium fluoride and 3vt% deionized water. In the solution, the titanium sheet is used as the positive electrode, and the graphite sheet is used as the negative electrode. Anodize at 60V for 4h, take out the titanium sheet and put it in deionized water for ultrasonication until the surface film falls off, rinse it with deionized water, Drying, continue anodizing at 60V for 6h, ultrasonication in ethylene glycol for 15min, annealing at 450°C for 2h at a heating rate of 2°C / min, to obtain titanium dioxide nanotube arrays in anatase phase. Graphene oxide was prepared according to the improved Hummers method, which was placed in a tube furnace with a flow rate of 40cc of argon gas, and the temperature was raised to 500°C at a rate of 2°C / min, and reduced graphene oxide was obtained after hold...

Embodiment 2

[0054] The preparation method of the titanium dioxide nanotube array of anatase phase is the same as that of Example 1. Graphene oxide was prepared according to the improved Hummers method, and the preparation method of graphene quantum dots (light yellow clear liquid) was the same as in Example 1.

[0055] The obtained titanium oxide nanotubes were placed in the obtained liquid, the titanium oxide was used as the positive electrode, and the platinum sheet was used as the negative electrode, and a voltage of 5 V was added to react for 8 hours to obtain a quantum dot-modified titanium oxide nanotube array. Dissolve 0.5g of potassium permanganate in 50mL of deionized water, immerse the quantum dot-modified titanium oxide nanotube array in the solution, drop in 200μL of concentrated sulfuric acid, put it in a water bath and keep it at 95°C for 30min to obtain quantum dot modification Manganese oxide / titanium oxide nanoarray materials (GQDs / TiO 2 @MnO 2 ). The obtained samples ...

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Abstract

The invention provides a graphene quantum dot modified manganese oxide / titanium oxide nanotube array material and a preparation method and application thereof, and belongs to the field of photocatalysis of film materials. A titanium dioxide material is composited and modified through graphene quantum dots and manganese oxide; compared with titanium dioxide materials, the titanium dioxide materialmodified with quantum dots have improved electrochemical properties; the compositing with manganese oxide enables absorbing boundary of titanium dioxide to be widened, forbidden band width of titaniumdioxide can be evidently decreased, the absorbing boundary is extended, titanium dioxide can utilize visible light more efficiently, compositing of photo-induced electrons and holes is inhibited, photocatalytic activity of titanium dioxide is improved, and hydrogen can be produced by photoelectric catalysis of titanium dioxide more efficiently; in addition, reduced graphene oxide and titanium sheeting are nontoxic and pollution free, the cost is low, and the preparation method has the advantages of simplicity, convenience and high speed; the morphology and properties are controlled by controlling reaction voltage and time and water bath reaction time, and the operation is simple.

Description

technical field [0001] The invention relates to the technical field of photocatalysis of thin film materials, in particular to a graphene quantum dot modified manganese oxide / titanium oxide nanotube array material and its preparation method and application. Background technique [0002] With the depletion of fossil fuels and increasingly serious environmental problems, it is imperative to find new alternative energy sources. Hydrogen, as a clean, efficient and renewable energy source, has become one of the current energy research hotspots. Since Fujishima and Honda discovered TiO in 1972 2 Since water can be decomposed into hydrogen and oxygen, the use of semiconductor materials as catalysts for hydrogen production by photolysis of water has attracted extensive attention. Among many semiconductor photocatalysts, TiO 2 Because of the advantages of safety, non-toxicity, low cost, high chemical stability, and high catalytic activity, it has become one of the first-choice mat...

Claims

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Application Information

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IPC IPC(8): B01J23/34C01B3/04
CPCY02E60/36
Inventor 张勇张曼茹吴玉程魏浩山秦永强舒霞崔接武王岩
Owner HEFEI UNIV OF TECH
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