CN104495918A - Method for preparing granular titanium dioxide/two-dimensional nano-titanium carbide composite material - Google Patents

Abstract

The invention provides a method for preparing a granular titanium dioxide/two-dimensional nano-titanium carbide composite material. The method comprises the following steps: preparing a high-purity ternary layered Ti3AlC2 ceramic block body by vacuum sintering, and grinding by virtue of a high-energy ball mill to obtain Ti3AlC2 ceramic powder which has a grain diameter of 8-75mu m; immersing the Ti3AlC2 ceramic powder in a hydrofluoric acid solution to stir, carrying out a corrosion reaction, and centrifugally washing to obtain a two-dimensional layered nano-material MXene-Ti3C2; finally, hydrolyzing with tetrabutyl titanate to generate TiO2 loaded MXene-Ti3C2 so as to obtain the TiO2/MXene-Ti3C2 nano-composite material. The method has the advantages of simple preparation process, controllable process and low cost. The TiO2/MXene-Ti3C2 nano-composite material has graphene-like two-dimensional layered characteristics, has the characteristics of uniform layer, large specific surface area, excellent conductivity, fine and uniformly distributed TiO2 particles, excellent photocatalytic performance, excellent biological affinity and the like, and is applicable to the fields of photocatalysis, wastewater treatment, lithium ion batteries, super capacitors, biosensors and other fields.

Description

The preparation method of particulate titanium dioxide/two-dimensional nano titanium carbide matrix material

Technical field

The invention belongs to nano-functional material preparation field, be specifically related to the preparation method of a kind of particulate state anatase titanium dioxide/two-dimensional nano titanium carbide (MXene) matrix material.

Background technology

Ti ₃alC ₂the mixture between a kind of special metal and pottery, simultaneously with metal and ceramic premium properties.Both there is metallicity, at normal temperatures, had good heat conductivility and conductivity, and had lower vickers microhardness and higher Young's modulus and shearing modulus, can mechanical workout be carried out, and at relatively high temperatures there is plasticity; There is again the performance of pottery simultaneously, have higher yield strength, high-melting-point, high thermal stability and good oxidation-resistance.Weed out the old and bring forth the new, by ternary layered Ti ₃alC ₂carry out corrosion research, thus form typical two dimensional crystal MXene-Ti ₃c ₂nano material.

Two-dimensional layer nano-carbide MXene-Ti ₃c ₂it is the material of a kind graphene-structured, ultra-thin two-dimension nanometer sheet has superpower catalytic performance, photovoltaic performance and chemical property due to the synusia thickness of the appearance structure of its uniqueness, less particle size, larger surface volume ratio and atom level, is widely used in function ceramics, photochemical catalysis, lithium ion battery, solar cell, gas sensor etc.

Nano titanium oxide has most valuable optical property, all demonstrates fine development prospect in automotive industry and numerous areas.Nano titanium oxide has very high chemical stability, thermostability, nontoxicity etc., is widely used in anti-ultraviolet material, photochemical catalysis catalyst, lithium cell etc.

The people such as week prepare graphene-based titanium dioxide nano composite material and have studied its photocatalytic activity, and experimental result shows, the photocatalytic activity of graphene-based titanium dioxide obviously strengthens; The people such as Michael Naguib adopt the method such as hydro-thermal and Quick Oxidation to prepare TiO ₂/ graphite nano composite material, and show that its performance in lithium ion battery, photochemical catalysis etc. is all better than single two-dimensional nano MXene-Ti ₃c ₂.

Therefore, anatase titanium dioxide/two-dimensional layer nano titanium carbide (MXene) matrix material, will be expected to there is good application in fields such as photochemical catalysis, wastewater treatment, lithium ion battery, ultracapacitor, biosensors.

Summary of the invention

In order to overcome the defect of above-mentioned prior art, the object of the invention is to generate TiO by tetrabutyl titanate hydrolysis ₂load to MXene-Ti ₃c ₂nano-material surface, thus the preparation method providing a kind of particulate state anatase titanium dioxide/two-dimensional nano titanium carbide (MXene) matrix material, by Ti ₃alC ₂in HF acid, carry out chemical etching, Al is etched away by selectivity, form a kind of two-dimensional layer material MXene-Ti ₃c ₂, then at two-dimensional layer material MXene-Ti ₃c ₂upper load TiO ₂, make MXene-Ti ₃c ₂obtain specific surface larger, take into account TiO ₂advantage, as photocatalysis performance, one's own physical property, pattern is various.

In order to achieve the above object, technical scheme of the present invention is as follows:

The preparation method of particulate state anatase titanium dioxide/two-dimensional nano titanium carbide matrix material, comprises the steps:

(1) by ternary layered Ti ₃alC ₂ceramic powder high-energy ball milling 1h-4h, rotating speed 400r/min, ball material mass ratio 10:1,40 DEG C-60 DEG C oven dry after refinement powder, obtain particle diameter at the Ti of 8 μm-75 μm ₃alC ₂ceramic powder;

(2) by gained Ti in step (1) ₃alC ₂ceramic powder is got 2g ~ 10g and is immersed in 50mL ~ 200mL35wt% ~ 45wt% hydrofluoric acid solution and reacts 6h ~ 120h; Stir, corrosion product is used deionized water eccentric cleaning, until centrifuged supernatant pH is between 5 ~ 6; Then washes of absolute alcohol is used 2 ~ 4 times; Gained solid sample is dry, obtain two-dimensional layer nano material MXene-Ti ₃c ₂;

(3) by step (2) gained two-dimensional nano MXene-Ti ₃c ₂get 150mg ~ 250mg and put into 200mL dehydrated alcohol, stir 0.5h, the tetrabutyl titanate of instillation 0.5mL ~ 2mL, continue to stir 6h, by dehydrated alcohol eccentric cleaning extremely without decomposes, then use deionized water eccentric cleaning, solid sample is dried, obtains TiO ₂/ MXene-Ti ₃c ₂matrix material.

Advantage of the present invention is to utilize simple chemical reaction tetrabutyl titanate hydrolysis, at room temperature produces TiO comparatively efficiently ₂load Balanced, the TiO that pattern is various ₂/ MXene-Ti ₃c ₂matrix material.TiO ₂load, improves single MXene-Ti ₃c ₂the various performances of powder, make it apply more extensive.For further in the application in the fields such as ultracapacitor, lithium ion battery, biosensor, nano adsorber, carry out the preparation work of precursor.

Accompanying drawing explanation

Fig. 1 is Ti ₃alC ₂before powder corrosion treatment, after corrosion treatment, and corrosion product MXene-Ti ₃c ₂load TiO ₂the XRD figure spectrum of sample.

Fig. 2 (a) is Ti ₃alC ₂the SEM figure of powder granule, Fig. 2 (b) is MXene-Ti after corrosion treatment ₃c ₂sEM figure, Fig. 2 (c) is TiO ₂/ MXene-Ti ₃c ₂the SEM figure of nano composite material, the local high power SEM that Fig. 2 (d) is Fig. 2 (c) schemes.

Embodiment

Further describe the present invention below by way of specific embodiments, the present invention also describes by other the scheme not departing from the technology of the present invention feature, and the change therefore within the scope of the present invention all or equivalent scope of the invention is all included in the invention.

Embodiment one

The present embodiment comprises the following steps:

(1) method of vacuum sintering is adopted to prepare highly purified ternary layered Ti ₃alC ₂ceramic powder, then high-energy ball milling powder 4h, rotating speed 400r/min, ball material mass ratio 10:1, after refinement powder, 60 DEG C of oven dry, are shown in Fig. 1 and Fig. 2 (a), and in Fig. 1, XRD figure spectrum describes the thing of gained powder is Ti mutually ₃alC ₂crystal, and foreign matter content is few, in Fig. 2 (a), SEM figure shows Ti ₃alC ₂the microscopic appearance of crystal, can find out that its grain size is about 8 μm, and obvious laminate structure;

(2) gained powder 5g in step (1) is immersed in 100mL, 40wt% hydrofluoric acid solution reacts 48h, stir, corrosion product is used deionized water eccentric cleaning, until centrifuged supernatant pH is between 5 ~ 6; Then washes of absolute alcohol is used 4 times; By gained solid sample drying at room temperature, obtain two-dimensional layer nano material MXene-Ti ₃c ₂, see Fig. 1, wherein XRD figure stave understands Ti ₃alC ₂the change of diffraction peak, contrasts with the XRD diffracting spectrum of Theoretical Calculation, successfully obtains MXene-Ti ₃c ₂powder thing phase.See Fig. 2 (b), wherein SEM figure shows MXene-Ti ₃c ₂microscopic appearance, can find out that its lamellar spacing is about 50nm, be typical two-dimensional layer nano material;

(3) by step (2) gained two-dimensional nano MXene-Ti ₃c ₂get 200mg and put into 200mL dehydrated alcohol, stir 0.5h, the tetrabutyl titanate of instillation 1mL, continue to stir 6h, by dehydrated alcohol eccentric cleaning extremely without decomposes, then use deionized water eccentric cleaning, solid sample is dried, obtains TiO ₂/ MXene-Ti ₃c ₂matrix material.See Fig. 1, wherein XRD figure stave understands Detitanium-ore-type TiO ₂crystal successfully loads to MXene-Ti ₃c ₂on powder.See Fig. 2 (c) and Fig. 2 (d), wherein SEM figure shows TiO ₂/ MXene-Ti ₃c ₂the microscopic appearance of matrix material, can find out TiO ₂size is about 25nm, and is evenly distributed, and loads to MXene-Ti well ₃c ₂in two-dimensional layer nano material, form novel TiO ₂/ MXene-Ti ₃c ₂nano composite material.

Embodiment two

The present embodiment comprises the following steps:

(1) method of vacuum sintering is adopted to prepare highly purified ternary layered Ti ₃alC ₂ceramic powder, then high-energy ball milling powder 1h, rotating speed 400r/min, ball material mass ratio 10:1, after refinement powder, 40 DEG C of oven dry, obtain Ti ₃alC ₂ceramic powder;

(2) be immersed in 50mL, 35wt% hydrofluoric acid solution by gained powder 2g in step (1) and react 6h, stir, washed with de-ionized water is about 5 ~ 6 to pH, washes of absolute alcohol 2 times, centrifugation, gained solid sample is dry, obtain two-dimensional layer MXene-Ti ₃c ₂nano material;

(3) by step (2) gained two-dimensional nano MXene-Ti ₃c ₂get 150mg and put into 200mL dehydrated alcohol, stir 0.5h, the tetrabutyl titanate of instillation 0.5mL, continue to stir 6h, by dehydrated alcohol eccentric cleaning extremely without decomposes, then use deionized water eccentric cleaning, solid sample is dried, obtains TiO ₂/ MXene-Ti ₃c ₂matrix material.

Embodiment three

The present embodiment comprises the following steps:

(1) method of vacuum sintering is adopted to prepare highly purified ternary layered Ti ₃alC ₂ceramic powder, then high-energy ball milling powder 3h, rotating speed 400r/min, ball material mass ratio 10:1,50 DEG C of oven dry after refinement powder;

(2) gained powder 3g in step (1) is immersed in 70mL, 35wt% hydrofluoric acid solution reacts 24h, stir, corrosion product is used deionized water eccentric cleaning, until centrifuged supernatant pH is between 5 ~ 6; Then washes of absolute alcohol is used 3 times; Gained solid sample is dry, obtain two-dimensional layer nano material MXene-Ti ₃c ₂;

(3) by step (2) gained two-dimensional nano MXene-Ti ₃c ₂get 150mg and put into 200mL dehydrated alcohol, stir 0.5h, the tetrabutyl titanate of instillation 1.5mL, continue to stir 6h, by dehydrated alcohol eccentric cleaning extremely without decomposes, then use deionized water eccentric cleaning, solid sample is dried, obtains TiO ₂/ MXene-Ti ₃c ₂matrix material.

Embodiment four

The present embodiment comprises the following steps:

(1) method of vacuum sintering is adopted to prepare highly purified ternary layered Ti ₃alC ₂ceramic powder, then high-energy ball milling powder 3h, rotating speed 400r/min, ball material mass ratio 10:1,50 DEG C of oven dry after refinement powder;

(2) gained powder 4g in step (1) is immersed in 90mL, 40wt% hydrofluoric acid solution reacts 48h, stir, corrosion product is used deionized water eccentric cleaning, until centrifuged supernatant pH is between 5 ~ 6; Then washes of absolute alcohol is used 4 times; Gained solid sample is dry, obtain two-dimensional layer nano material MXene-Ti ₃c ₂;

(3) by step (2) gained two-dimensional nano MXene-Ti ₃c ₂get 200mg and put into 200mL dehydrated alcohol, stir 0.5h, the tetrabutyl titanate of instillation 2mL, continue to stir 6h, by dehydrated alcohol eccentric cleaning extremely without decomposes, then use deionized water eccentric cleaning, solid sample is dried, obtains TiO ₂/ MXene-Ti ₃c ₂matrix material.

Claims (1)

1. the preparation method of particulate state anatase titanium dioxide/two-dimensional nano titanium carbide matrix material, is characterized in that, comprise the steps:

(1) by ternary layered Ti ₃alC ₂ceramic powder high-energy ball milling 1h-4h, rotating speed 400r/min, ball material mass ratio 10:1,40 DEG C-60 DEG C oven dry after refinement powder, obtain particle diameter at the Ti of 8 μm-75 μm ₃alC ₂ceramic powder;

(2) by gained Ti in step (1) ₃alC ₂ceramic powder is got in 2g ~ 10g submergence 50mL ~ 200mL35wt% ~ 45wt% hydrofluoric acid solution and is reacted 6h ~ 120h; Stir, corrosion product is used deionized water eccentric cleaning, until centrifuged supernatant pH is between 5 ~ 6; Then washes of absolute alcohol is used 2 ~ 4 times; Gained solid sample is dry, obtain two-dimensional layer nano material MXene-Ti ₃c ₂;

(3) by step (2) gained two-dimensional nano MXene-Ti ₃c ₂get 150mg ~ 250mg and put into 200mL dehydrated alcohol, stir 0.5h, the tetrabutyl titanate of instillation 0.5mL ~ 2mL, continue to stir 6h, by dehydrated alcohol eccentric cleaning extremely without decomposes, then use deionized water eccentric cleaning, solid sample is dried, obtains TiO ₂/ MXene-Ti ₃c ₂matrix material.