CN110372034A - A kind of preparation method of two-dimensional layer black titanium dioxide - Google Patents

A kind of preparation method of two-dimensional layer black titanium dioxide Download PDF

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Publication number
CN110372034A
CN110372034A CN201910516183.5A CN201910516183A CN110372034A CN 110372034 A CN110372034 A CN 110372034A CN 201910516183 A CN201910516183 A CN 201910516183A CN 110372034 A CN110372034 A CN 110372034A
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dimensional layer
titanium dioxide
layer black
preparation
black titanium
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蒋海英
钱婧
赵森
解兴隆
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Northwest University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063Titanium; Oxides or hydroxides thereof
    • B01J35/39
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00Compounds of titanium
    • C01G23/04Oxides; Hydroxides
    • C01G23/047Titanium dioxide
    • C01G23/08Drying; Calcining ; After treatment of titanium oxide
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/20Two-dimensional structures
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/70Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/80Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM

Abstract

The invention discloses a kind of preparation methods of two-dimensional layer black titanium dioxide, using New Two Dimensional stratiform Ti3C2 MXenes material, only can prepare the black titanium dioxide (TiO2) with two-dimensional layered structure by step heat treatment.Concrete operations are as follows: a certain amount of Ti3C2 MXenes powder being taken to be placed in high temperature furnace, certain temperature is heated to by room temperature with specific heating rate, and the regular hour is kept at such a temperature, to sample cooled to room temperature, it can be prepared by two-dimensional layer black TiO2.This method is not related to any harsh dangerous condition, raw materials used Ti3C2 MXenes only simple and easy to get, be not related to because reaction ratio it is improper caused by produce waste, it is not related to later period separating step yet, reaction condition is simple, production cost is low, can stablize a large amount of uniform preparations for realizing two-dimensional layer black titanium dioxide, and the safety and reliability of production process greatly improves.

Description

A kind of preparation method of two-dimensional layer black titanium dioxide
Technical field
The invention belongs to inorganic nano photocatalyst material technical field, in particular to a kind of two-dimensional layer black titanium dioxide The preparation method of titanium.
Background technique
From Fujishima and Honda in 1972 take the lead on semiconductor TiO2 electrode find photocatalytic cleavage water reaction with Come, photocatalysis is just used as an emerging cross discipline technology, be applied in various fields: (1) hydrogen manufacturing of photocatalytic cleavage water/ Oxygen;(2) photocatalysis degradation organic contaminant;(3) photocatalysis organic synthesis;(4) photo catalytic reduction CO2 produces methane;(5) light Catalytic activation methane produces methanol;(6) photo catalytic reduction nitrogen synthesis ammonia etc..And titanium dioxide (TiO2) is as photocatalysis half The representative materials of conductor suffer from performance very outstanding in the every field of photocatalysis technology application, therefore TiO2 also one It is considered as directly one of the ideal material for solving energy shortage and two big world property problem of environmental pollution, receives vast scientific research work The favor of author and industry.
Up to the present, restricting TiO2 photocatalysis technology to develop maximum bottleneck is exactly utilization of the semiconductor to sunlight Rate, and influencing semiconductor mainly has two big factors to sun light utilization efficiency: the first, the forbidden bandwidth of TiO2 it is wide (anatase: 3.2 eV;Rutile: 3.0eV), the ultraviolet light for accounting for sunlight~5% can only be absorbed, visible light and near infrared light can not be utilized Energy;The second, for TiO2 as a kind of semiconductor, intrinsic electric conductivity is not high, and crystal structure is unfavorable for photohole-electricity The separation and transmission of son pair.Therefore, to raising TiO2 to the utilization rate of sunlight, it is necessary to expand it to visible light and near-infrared The responding ability of light, while improving the separated transmission efficiency of its electron-hole pair.
2011, it is (black that Samuel Mao etc. reports a kind of low temperature preparation black nano titanium dioxide on " Science " Titanium) method, cause everybody very big concern.It is reported that 5 days at High Pressure Hydrogen atmosphere and 200 DEG C can be obtained defect project The photocatalytic activity of titanium dioxide nano material, the black titanium dioxide of preparation is improved significantly.Black TiO2 can inhale Receiving portions visible light and infrared light, main cause are that the defect that its internal structure is formed under this condition results in titanium dioxide The variation of optical property and band structure.In view of the excellent performance that black TiO2 is shown in terms of photocatalysis, vast scientific research Worker breaks through photocatalysis technology bottleneck to the material and places high hopes, and industry also expects to this, waits and sees.
Mainly have about the preparation method of black TiO2 at present: H2 press over system, TiH2/NaBH4 reduction method, carbon reduction method etc. Deng.But the preparation condition of these methods is mostly more harsh, be related to the hazardous gases such as high pressure or vacuum environment, hydrogen use, Use, use of inert gas of the hazardous reactions object such as metal hydride etc., this undoubtedly gives the industrialized production band of black TiO2 Carry out difficulty centainly, not only increased production cost, and reduced the safety of production process, is not able to satisfy industrial production Demand.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of two-dimensional layer black titanium dioxide, to solve above-mentioned background The problem of being proposed in technology.
To achieve the above object, the invention provides the following technical scheme:
A kind of preparation method of two-dimensional layer black titanium dioxide, step 1: Ti3AlC2 ceramics being etched by HF and obtain two Tie up stratiform Ti3C2MXenes powder;
Step 2: the two-dimensional layer Ti3C2MXenes powder obtained in step 1 is placed in be processed in high temperature furnace, high temperature furnace Inside filling gas is air;
Step 3: high temperature furnace internal temperature is increased in turn to two-dimensional layer by target temperature with specific heating rate Ti3C2 MXenes powder is heat-treated, and goal temperature is 200 DEG C -900 DEG C, the inner and holding at target temperature - 120 minutes 10 minutes;
Step 4: stopping is internally heated high temperature furnace, is allowed to natural cooling, obtained two-dimensional layer black TiO2.
As a further solution of the present invention: specific heating rate is 5 DEG C -20 DEG C/min in step 3.
As a further solution of the present invention: target temperature is 300 DEG C -600 DEG C in step 3.
As a further solution of the present invention: being kept for -60 minutes 10 minutes at target temperature in step 3.
As a further solution of the present invention: target temperature is 400 DEG C in step 3.
As a further solution of the present invention: being kept for 30 minutes at target temperature in step 3.
Compared with prior art, cheap the beneficial effects of the present invention are: raw material of the present invention is simple and easy to get, it can meet High-volume industrial production.
Reaction condition of the present invention is mild, and heat treatment in the process carries out under normal pressure, and it is severe not to be related to high pressure/vacuum environment etc. The hazardous reactions objects such as inert gases, the metal hydrides such as inflammable and explosive hazardous gas, the nitrogen/argon gas such as quarter property condition, hydrogen, it is raw It is reliable to produce process safety.
Operation of the present invention is easy, and step preparation is not related to later period separating step, is greatly improved production efficiency, reduces life Produce cost.
From the foregoing, it will be observed that the black TiO2 with two-dimensional layered structure can be simply, easily made in the present invention, this method is former Expect cheap and easy to get, easy to operate, safe preparation process is reliable, is suitable for industry's enlarging production, have a good application prospect and Wide market.
Detailed description of the invention
Fig. 1 is the photo of two-dimensional layer black TiO2 sample in the present invention.
Fig. 2 is the scanning electron microscopic picture of the two-dimensional layer black TiO2 sample prepared in the present invention.
Fig. 3 is the X-ray powder diffraction spectrogram of the two-dimensional layer black TiO2 sample prepared in the present invention.
Fig. 4 is the UV-Vis DRS spectrogram of the two-dimensional layer black TiO2 sample prepared in the present invention.
Fig. 5 be in the present invention target temperature be 400 DEG C, handle the time 10 minutes two-dimensional layer black TiO2 sample photograph Piece.
Fig. 6 be in the present invention target temperature be 400 DEG C, handle the time 40 minutes two-dimensional layer black TiO2 sample photograph Piece.
Fig. 7 is that target temperature is 400 DEG C, handles the time 120 minutes two-dimensional layer black TiO2 samples in the present invention Photo
Fig. 8 is that target temperature is 500 DEG C, handles the time 120 minutes two-dimensional layer black TiO2 samples in the present invention Photo
Fig. 9 is that target temperature is 600 DEG C, handles the time 120 minutes two-dimensional layer black TiO2 samples in the present invention Photo.
Specific embodiment
In the description of the present invention, it is to be understood that, term " center ", " longitudinal direction ", " transverse direction ", "upper", "lower", The orientation or positional relationship of the instructions such as "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outside" is It is based on the orientation or positional relationship shown in the drawings, is merely for convenience of description of the present invention and simplification of the description, rather than instruction or dark Show that signified device or element must have a particular orientation, be constructed and operated in a specific orientation, therefore should not be understood as pair Limitation of the invention.In addition, term " first ", " second " etc. are used for description purposes only, it is not understood to indicate or imply phase To importance or implicitly indicate the quantity of indicated technical characteristic.The feature for defining " first ", " second " etc. as a result, can To explicitly or implicitly include one or more of the features.In the description of the present invention, unless otherwise indicated, " multiple " It is meant that two or more.
In the description of the present invention, it should be noted that unless otherwise clearly defined and limited, term " installation ", " phase Even ", " connection " shall be understood in a broad sense, for example, it may be being fixedly connected, may be a detachable connection, or be integrally connected;It can To be mechanical connection, it is also possible to be electrically connected;It can be directly connected, can also can be indirectly connected through an intermediary Connection inside two elements.For the ordinary skill in the art, above-mentioned term can be understood by concrete condition Concrete meaning in the present invention.
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other Embodiment shall fall within the protection scope of the present invention.
Please refer to Fig. 1-9, in the embodiment of the present invention, a kind of preparation method of two-dimensional layer black titanium dioxide, including with Lower step:
Step 1: Ti3AlC2 ceramics being etched by HF and obtain two-dimensional layer Ti3C2MXenes powder;
Step 2: the two-dimensional layer Ti3C2MXenes powder obtained in step 1 is placed in be processed in high temperature furnace, high temperature furnace Inside filling gas is air;
Step 3: high temperature furnace internal temperature is increased in turn to two-dimensional layer by target temperature with specific heating rate Ti3C2 MXenes powder is heat-treated, and goal temperature is 200 DEG C -900 DEG C, preferably 300 DEG C -600 DEG C, best It is in 500 DEG C, and keeps -120 minutes 10 minutes, preferably -60 minutes 10 minutes, preferably 30 points at target temperature Clock;
Step 4: stopping is internally heated high temperature furnace, is allowed to natural cooling, obtains two-dimensional layer black TiO2, made Standby two-dimensional layer black TiO2 is in UV-Vis DRS experiment it can be seen that prepared black titanium dioxide is visible Near infrared region has photoresponse (shown in Fig. 4), that is, shows that the product is target product.
Two-dimensional layer Ti3C2MXenes powder is placed in high temperature furnace and is heat-treated, two-dimensional layer black is directly obtained TiO2。
Its synthesis process follows following chemical equation:
Ti3C2(s)+5O2(g)→3TiO2(s)+2CO2(g);
Obtained two-dimensional layer black TiO2 crystal phase is single anatase.
Obtained two-dimensional layer black TiO2 is macroscopically the powder of black, microcosmic upper for two-dimensional layer nanometer sheet knot Structure.
The present invention proposes that a kind of raw material is simple and easy to get, synthesis step is brief, safe operation preparation method, to obtain There must be the black titanium dioxide of two-dimensional layered structure.The black titanium dioxide of this method preparation not only includes a large amount of and continuous Adjustable oxygen defect concentration due also to using special precursor --- the Ti3C2MXenes of two-dimensional layer when preparation, and has Be conducive to the two-dimensional layered structure of charge transmission.Process of the present invention is not related to any harsh dangerous condition (such as high pressure/vacuum The danger such as inert gases, the metal hydrides such as the inflammable and explosive hazardous gases such as the harshness condition such as environment, hydrogen, nitrogen/argon gas Reactant), raw materials used only Ti3C2MXenes simple and easy to get, be not related to because reaction ratio it is improper caused by produce wave Take, be not also related to later period separating step, reaction condition is simple, and production cost is low, can stablize and realize two-dimensional layer black dioxy Change a large amount of uniform preparations of titanium, the safety and reliability of production process greatly improves.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims Variation is included within the present invention.Any reference signs in the claims should not be construed as limiting the involved claims.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art The other embodiments being understood that.

Claims (6)

1. a kind of preparation method of two-dimensional layer black titanium dioxide, which comprises the following steps:
Step 1: Ti3AlC2 ceramics being etched by HF and obtain two-dimensional layer Ti3C2 MXenes powder;
Step 2: the two-dimensional layer Ti3C2 MXenes powder obtained in step 1 is placed in it is to be processed in high temperature furnace, in high temperature furnace It is air that gas is filled in portion;
Step 3: high temperature furnace internal temperature is increased in turn to two-dimensional layer by target temperature with specific heating rate Ti3C2MXenes powder is heat-treated, and goal temperature is 200 DEG C -900 DEG C, and 10 are kept at target temperature - 120 minutes minutes;
Step 4: stopping is internally heated high temperature furnace, is allowed to natural cooling, obtains two-dimensional layer black TiO2.
2. the preparation method of two-dimensional layer black titanium dioxide according to claim 1, which is characterized in that special in step 3 Fixed heating rate is 5 DEG C -20 DEG C/min.
3. the preparation method of two-dimensional layer black titanium dioxide according to claim 1, which is characterized in that mesh in step 3 Marking temperature is 300 DEG C -600 DEG C.
4. the preparation method of two-dimensional layer black titanium dioxide according to claim 1, which is characterized in that mesh in step 3 It is kept for -60 minutes 10 minutes at mark temperature.
5. the preparation method of two-dimensional layer black titanium dioxide according to claim 3, which is characterized in that mesh in step 3 Marking temperature is 400 DEG C.
6. the preparation method of two-dimensional layer black titanium dioxide according to claim 4, which is characterized in that mesh in step 3 It is kept for 30 minutes at mark temperature.
CN201910516183.5A 2019-06-14 2019-06-14 A kind of preparation method of two-dimensional layer black titanium dioxide Pending CN110372034A (en)

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CN112933958A (en) * 2021-02-10 2021-06-11 广西大学 Method for photocatalytic carbon dioxide reduction
CN114940490A (en) * 2022-04-08 2022-08-26 合肥工业大学 Preparation method of carbon nano tube/titanium dioxide flexible composite membrane

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CN111233037A (en) * 2020-01-19 2020-06-05 济南大学 Nb-shaped alloy2O5Preparation method and application of nanorod
CN111233037B (en) * 2020-01-19 2022-05-06 济南大学 Nb-shaped alloy2O5Preparation method and application of nanorod
CN112933958A (en) * 2021-02-10 2021-06-11 广西大学 Method for photocatalytic carbon dioxide reduction
CN112933958B (en) * 2021-02-10 2023-06-06 广西大学 Method for reducing carbon dioxide by photocatalysis
CN114940490A (en) * 2022-04-08 2022-08-26 合肥工业大学 Preparation method of carbon nano tube/titanium dioxide flexible composite membrane

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