CN108816264A - A kind of ultra-thin g-C3N4The TiO of covering2Dysmorphism array film and preparation method thereof - Google Patents

A kind of ultra-thin g-C3N4The TiO of covering2Dysmorphism array film and preparation method thereof Download PDF

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CN108816264A
CN108816264A CN201810569379.6A CN201810569379A CN108816264A CN 108816264 A CN108816264 A CN 108816264A CN 201810569379 A CN201810569379 A CN 201810569379A CN 108816264 A CN108816264 A CN 108816264A
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tio
dysmorphism
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array
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CN108816264B (en
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王德宝
李洪浩
宋彩霞
耿世泽
周艳红
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Qingdao Zhonghai Blue Marine Biological Resources Development Co ltd
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Qingdao University of Science and Technology
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Abstract

The invention discloses a kind of ultra-thin g-C3N4The TiO of covering2Dysmorphism array film and preparation method thereof.It is characterized in that, the film is by ultra-thin g-C3N4The rutile TiO of covering2The TiO of nanometer stick array and two kinds of dysmorphisms of spike cluster2Nanostructure height is staggeredly constituted, and the method is using inorganic titanium sulfate as raw material, in acid condition, goes out precursor thin-film in FTO deposition on glass by a step hydro-thermal reaction, then be fired, obtains rutile TiO2Dysmorphism array film recycles melamine to decompose the gas generated through chemical vapor deposition in TiO2One layer of ultra-thin curling g-C is deposited on dysmorphism array film3N4.Preparation method of the present invention is easy to operate, and reaction condition is mild, and as optoelectronic pole, degradation of organic dyes, photoelectrocatalysis water decomposition hydrogen preparation field have important application prospect in photoelectrocatalysis water.

Description

A kind of ultra-thin g-C3N4The TiO of covering2Dysmorphism array film and preparation method thereof
Technical field
The invention belongs to photoelectrocatalysimaterial material fields, are related to a kind of ultra-thin g-C3N4The TiO of covering2Dysmorphism array is thin The preparation method of film, specifically, being to be related to ultra-thin g-C3N4The TiO of covering2Dysmorphism array film photoelectrocatalysimaterial material Preparation method.
Background technique
Rutile TiO2Intrinsic semiconductor forbidden bandwidth be 3.0eV, light absorption is concentrated mainly on ultra-violet (UV) band, to visible Photoresponse is poor, and there is a problem of that photo-generate electron-hole is high to recombination rate low with quantum efficiency, and this strongly limits TiO2? The application of photocatalysis field.g-C3N4Forbidden bandwidth be 2.7e V, it is environmentally friendly and excellent to have controllable band gap width Thermal stability has response to visible light.By g-C3N4And TiO2It is compound, be conducive to widen photoresponse, reduce photo-generate electron-hole Pair it is compound, greatly improve photocatalysis efficiency.Currently, g-C3N4Preparation method mainly have thermal polycondensation process.It is usual using thermal polymerization method Obtain the g-C of bulk structure3N4, specific surface area is small, and active site is few.It needs using chemical stripping method or liquid phase ultrasound stripping method, It can just obtain thin nanometer sheet, it is complex for operation step, charge stripping efficiency is low, low yield, it is difficult to prepare the ultrathin nanometer of large area Piece.Prepare the g-C of large area3N4Ultrathin nanometer piece is conducive to improve light utilization efficiency.
Summary of the invention
The present invention is directed to existing preparation g-C3N4/TiO2Synthesis process complexity, severe reaction conditions, be difficult to prepare big face The disadvantages of long-pending ultrathin nanometer piece, a kind of ultra-thin g-C is disclosed3N4The TiO of covering2Dysmorphism array film and preparation method thereof. It is characterized in that, the film is by ultra-thin curling g-C3N4The rutile TiO of covering2Nanometer stick array with two kinds of spike cluster The nanostructure of dysmorphism is constituted, and the method is anti-by a step hydro-thermal in acid condition using inorganic titanium sulfate as raw material Roasting technique again is answered, in FTO glass surface growing rutile type TiO2Dysmorphism array film recycles melamine to decompose The gas of generation is through chemical vapor deposition in TiO2One layer of ultra-thin curling g-C is deposited on dysmorphism array film3N4.The present invention It is achieved using following technical scheme：
(1) pretreatment of FTO glass：By FTO glass-cutting at specification be 1cm × 2.5cm small pieces, then it is successively soaked Enter into acetone, dehydrated alcohol, deionized water, respectively ultrasound 2-5min, after sufficiently cleaning up, in 70 DEG C of dry 2h.
(2)TiO2Nanometer rods and the staggered preparation of spike cluster：The titanium sulfate of 0.2-0.3g is dissolved in deionization In water, 4-8ml concentrated hydrochloric acid is then added, is made into the mixed solution of 20ml homogeneous transparent.Mixed solution is transferred to poly- four In the autoclave of vinyl fluoride liner, then in the solution by the pretreated two panels FTO glass opposed vertical placement of step (1), Then autoclave is sealed, heats 1-12h at 120-200 DEG C.After reaction, it by autoclave cooled to room temperature, takes FTO glass out is successively cleaned three times with deionized water and ethyl alcohol, in 70 DEG C of dry 2h.Dry FTO glass is finally put into pipe In formula furnace, it is warming up to 500-600 DEG C with the heating rate of 1-10 DEG C/min, 1-4h is kept the temperature, obtains TiO2Nanometer rods and spike stick Beam dysmorphism array film.
(3) TiO will be grown2The FTO electro-conductive glass of dysmorphism array film is placed in reaction tank, and reaction tank is put into appearance In device, 100-300mg melamine (urea or dicyandiamide) is taken to be put into container, it is closed.Be put into tube furnace with 2-10 DEG C/ The speed of min is raised to 500 DEG C -600 DEG C, keeps the temperature 1-3h.
It is an advantage of the current invention that the g-C of large area can be prepared3N4Ultra-thin curling nanometer sheet, and ultra-thin curling nanometer sheet Thickness is adjustable.Prepare the g-C of large area3N4Ultra-thin curling nanometer sheet is conducive to improve the utilization rate of visible light, while improving pair The transmitance of ultraviolet light, it is ensured that TiO2Make full use of ultraviolet light, and the large area g-C prepared3N4Ultra-thin curling nanometer sheet and TiO2 Nanometer rods and the contact area of spike cluster dysmorphism array increase, and are conducive to the separative efficiency for improving photo-generated carrier；It should Rutile TiO prepared by method2The nanostructure of nanometer stick array and two kinds of dysmorphisms of spike cluster has hetero-junctions Structure can be further improved TiO2PhotoelectrocatalytiPerformance Performance.It applies and is electrolysed organic dyestuff light in aquatic products hydrogen and water in photocatalysis Electrocatalysis Degradation field shows excellent catalytic performance.
Detailed description of the invention
Fig. 1 is ultra-thin g-C obtained by embodiment one3N4The TiO of covering2The XRD of dysmorphism array film sample is composed Figure.
Fig. 2 is TiO obtained by embodiment one2Dysmorphism array film sample and ultra-thin g-C3N4The TiO of covering2Together The SEM photograph of matter abnormity array film sample.
Fig. 3 is ultra-thin g-C obtained by embodiment one3N4The TiO of covering2Dysmorphism array film sample photoelectrochemical degradation The UV-Vis absorption spectrum of rhodamine B solution.
Specific embodiment
Below by embodiment, invention is further described in detail：
Embodiment one：
(1) it is 10mm × 25mm small pieces at specification by FTO glass-cutting, then it is successively immersed in acetone, anhydrous second In alcohol, deionized water, difference ultrasound 2min, after sufficiently cleaning up, in 70 DEG C of dry 2h.
(2) titanium sulfate of 0.24g is dissolved in deionized water, 5ml concentrated hydrochloric acid is then added, is made into 20ml homogeneous transparent Mixed solution.Mixed solution is transferred in the autoclave with polytetrafluoroethyllining lining, then step (1) is pre-processed Two panels FTO glass opposed vertical place in the solution, then autoclave is sealed, heats 2h at 180 DEG C.Reaction terminates Afterwards, by autoclave cooled to room temperature, FTO glass is taken out, is successively cleaned three times with deionized water and ethyl alcohol, in 70 DEG C of dryings 2h.Finally dry FTO glass is put into tube furnace, 500 DEG C is warming up to the heating rate of 10 DEG C/min, keeps the temperature 2h, obtain To TiO2Nanometer rods and the staggered film of spike cluster paramorph.
(3) TiO will be grown2The FTO electro-conductive glass of dysmorphism array film is placed in reaction tank, and reaction tank is put into appearance In device, 250mg melamine is taken to be put into container, it is closed.It is put into tube furnace and is raised to 500 DEG C with the speed of 10 DEG C/min, protect Warm 2h.
Embodiment two：
(1) it is 10mm × 25mm small pieces at specification by FTO glass-cutting, then it is successively immersed in acetone, anhydrous second In alcohol, deionized water, difference ultrasound 2min, after sufficiently cleaning up, in 70 DEG C of dry 2h.
(2) titanium sulfate of 0.24g is dissolved in deionized water, 5ml concentrated hydrochloric acid is then added, is made into 20ml homogeneous transparent Mixed solution.Mixed solution is transferred in the autoclave with polytetrafluoroethyllining lining, then step (1) is pre-processed Two panels FTO glass opposed vertical place in the solution, then autoclave is sealed, heats 2h at 180 DEG C.Reaction terminates Afterwards, by autoclave cooled to room temperature, FTO glass is taken out, is successively cleaned three times with deionized water and ethyl alcohol, in 70 DEG C of dryings 2h.Finally dry FTO glass is put into tube furnace, 500 DEG C is warming up to the heating rate of 10 DEG C/min, keeps the temperature 2h, obtain To TiO2Nanometer rods and the staggered film of spike cluster paramorph.
(3) TiO will be grown2The FTO electro-conductive glass of dysmorphism array film is placed in reaction tank, and reaction tank is put into appearance In device, 250mg melamine is taken to be put into container, it is closed.It is put into tube furnace and is raised to 550 DEG C with the speed of 10 DEG C/min, protect Warm 2h.
Embodiment three：
(1) it is 10mm × 25mm small pieces at specification by FTO glass-cutting, then it is successively immersed in acetone, anhydrous second In alcohol, deionized water, difference ultrasound 2min, after sufficiently cleaning up, in 70 DEG C of dry 2h.
(2) titanium sulfate of 0.24g is dissolved in deionized water, 5ml concentrated hydrochloric acid is then added, is made into 20ml homogeneous transparent Mixed solution.Mixed solution is transferred in the autoclave with polytetrafluoroethyllining lining, then step (1) is pre-processed Two panels FTO glass opposed vertical place in the solution, then autoclave is sealed, heats 1h at 180 DEG C.Reaction terminates Afterwards, by autoclave cooled to room temperature, FTO glass is taken out, is successively cleaned three times with deionized water and ethyl alcohol, in 70 DEG C of dryings 2h.Finally dry FTO glass is put into tube furnace, 500 DEG C is warming up to the heating rate of 10 DEG C/min, keeps the temperature 2h, obtain To TiO2Nanometer rods and the staggered film of spike cluster paramorph.
(3) TiO will be grown2The FTO electro-conductive glass of dysmorphism array film is placed in reaction tank, and reaction tank is put into appearance In device, 250mg melamine is taken to be put into container, it is closed.It is put into tube furnace and is raised to 500 DEG C with the speed of 10 DEG C/min, protect Warm 1h.
Example IV：
(1) it is 10mm × 25mm small pieces at specification by FTO glass-cutting, then it is successively immersed in acetone, anhydrous second In alcohol, deionized water, difference ultrasound 2min, after sufficiently cleaning up, in 70 DEG C of dry 2h.
(2) titanium sulfate of 0.24g is dissolved in deionized water, 5ml concentrated hydrochloric acid is then added, is made into 20ml homogeneous transparent Mixed solution.Mixed solution is transferred in the autoclave with polytetrafluoroethyllining lining, then step (1) is pre-processed Two panels FTO glass opposed vertical place in the solution, then autoclave is sealed, heats 6h at 150 DEG C.Reaction terminates Afterwards, by autoclave cooled to room temperature, FTO glass is taken out, is successively cleaned three times with deionized water and ethyl alcohol, in 70 DEG C of dryings 2h.Finally dry FTO glass is put into tube furnace, 500 DEG C is warming up to the heating rate of 5 DEG C/min, keeps the temperature 2h, obtain TiO2Nanometer rods and the staggered film of spike cluster paramorph.
(3) TiO will be grown2The FTO electro-conductive glass of dysmorphism array film is placed in reaction tank, and reaction tank is put into appearance In device, 100mg melamine is taken to be put into container, it is closed.It is put into tube furnace and is raised to 500 DEG C with the speed of 10 DEG C/min, protect Warm 2h.
Embodiment five：
(1) it is 10mm × 25mm small pieces at specification by FTO glass-cutting, then it is successively immersed in acetone, anhydrous second In alcohol, deionized water, difference ultrasound 2min, after sufficiently cleaning up, in 70 DEG C of dry 2h.
(2) titanium sulfate of 0.24g is dissolved in deionized water, 5ml concentrated hydrochloric acid is then added, is made into 20ml homogeneous transparent Mixed solution.Mixed solution is transferred in the autoclave with polytetrafluoroethyllining lining, then step (1) is pre-processed Two panels FTO glass opposed vertical place in the solution, then autoclave is sealed, heats 2h at 200 DEG C.Reaction terminates Afterwards, by autoclave cooled to room temperature, FTO glass is taken out, is successively cleaned three times with deionized water and ethyl alcohol, in 70 DEG C of dryings 2h.Finally dry FTO glass is put into tube furnace, 500 DEG C is warming up to the heating rate of 2 DEG C/min, keeps the temperature 1h, obtain TiO2Nanometer rods and the staggered film of spike cluster paramorph.
(3) TiO will be grown2The FTO electro-conductive glass of dysmorphism array film is placed in reaction tank, and reaction tank is put into appearance In device, 300mg melamine is taken to be put into container, it is closed.It is put into tube furnace and is raised to 500 DEG C with the speed of 10 DEG C/min, protect Warm 1h.
Embodiment six：
(1) it is 10mm × 25mm small pieces at specification by FTO glass-cutting, then it is successively immersed in acetone, anhydrous second In alcohol, deionized water, difference ultrasound 5min, after sufficiently cleaning up, in 70 DEG C of dry 2h.
(2) titanium sulfate of 0.3g is dissolved in deionized water, 6ml concentrated hydrochloric acid is then added, is made into 20ml homogeneous transparent Mixed solution.Mixed solution is transferred in the autoclave with polytetrafluoroethyllining lining, then step (1) is pre-processed Two panels FTO glass opposed vertical place in the solution, then autoclave is sealed, heats 3h at 180 DEG C.Reaction terminates Afterwards, by autoclave cooled to room temperature, FTO glass is taken out, is successively cleaned three times with deionized water and ethyl alcohol, in 70 DEG C of dryings 2h.Finally dry FTO glass is put into tube furnace, 500 DEG C is warming up to the heating rate of 10 DEG C/min, keeps the temperature 4h, obtain To TiO2Nanometer rods and the staggered film of spike cluster paramorph.
(3) TiO will be grown2The FTO electro-conductive glass of dysmorphism array film is placed in reaction tank, and reaction tank is put into appearance In device, 200mg melamine is taken to be put into container, it is closed.It is put into tube furnace and is raised to 500 DEG C with the speed of 10 DEG C/min, protect Warm 3h.
Embodiment seven：
(1) it is 10mm × 25mm small pieces at specification by FTO glass-cutting, then it is successively immersed in acetone, anhydrous second In alcohol, deionized water, difference ultrasound 2min, after sufficiently cleaning up, in 70 DEG C of dry 2h.
(2) titanium sulfate of 0.24g is dissolved in deionized water, 5ml concentrated hydrochloric acid is then added, is made into 20ml homogeneous transparent Mixed solution.Mixed solution is transferred in the autoclave with polytetrafluoroethyllining lining, then step (1) is pre-processed Two panels FTO glass opposed vertical place in the solution, then autoclave is sealed, heats 2h at 180 DEG C.Reaction terminates Afterwards, by autoclave cooled to room temperature, FTO glass is taken out, is successively cleaned three times with deionized water and ethyl alcohol, in 70 DEG C of dryings 2h.Finally dry FTO glass is put into tube furnace, 500 DEG C is warming up to the heating rate of 10 DEG C/min, keeps the temperature 2h, obtain To TiO2Nanometer rods and the staggered film of spike cluster paramorph.
(3) TiO will be grown2The FTO electro-conductive glass of dysmorphism array film is placed in reaction tank, and reaction tank is put into appearance In device, 400mg urea is taken to be put into container, it is closed.It is put into tube furnace and is raised to 500 DEG C with the speed of 5 DEG C/min, keep the temperature 2h.
Embodiment eight：
(1) it is 10mm × 25mm small pieces at specification by FTO glass-cutting, then it is successively immersed in acetone, anhydrous second In alcohol, deionized water, difference ultrasound 2min, after sufficiently cleaning up, in 70 DEG C of dry 2h.
(2) titanium sulfate of 0.24g is dissolved in deionized water, 5ml concentrated hydrochloric acid is then added, is made into 20ml homogeneous transparent Mixed solution.Mixed solution is transferred in the autoclave with polytetrafluoroethyllining lining, then step (1) is pre-processed Two panels FTO glass opposed vertical place in the solution, then autoclave is sealed, heats 2h at 180 DEG C.Reaction terminates Afterwards, by autoclave cooled to room temperature, FTO glass is taken out, is successively cleaned three times with deionized water and ethyl alcohol, in 70 DEG C of dryings 2h.Finally dry FTO glass is put into tube furnace, 500 DEG C is warming up to the heating rate of 10 DEG C/min, keeps the temperature 2h, obtain To TiO2Nanometer rods and the staggered film of spike cluster paramorph.
(3) TiO will be grown2The FTO electro-conductive glass of dysmorphism array film is placed in reaction tank, and reaction tank is put into appearance In device, 400mg dicyandiamide is taken to be put into container, it is closed.It is put into tube furnace and is raised to 500 DEG C with the speed of 10 DEG C/min, heat preservation 2h。
Fig. 1 is ultra-thin g-C obtained by embodiment one3N4The TiO of covering2The XRD of dysmorphism array film sample is composed Figure.As can be seen from the figure in addition to the diffraction of the FTO glass stannic oxide determined according to standard diffraction JCPDS No.46-1088 Outside peak, it is rutile phase TiO that remaining diffraction maximum, which corresponds to,2(101) crystal face and (002) crystal face diffraction maximum (JCPDS No.21-1276), but g-C is not detected3N4Apparent diffraction maximum, it may be possible to due to g-C3N4Crystallinity it is lower.
Fig. 2 a is TiO obtained by embodiment one2The SEM photograph of dysmorphism array film sample.It can from Fig. 2 a photo To find out, TiO2Nanometer rods dense growth is in FTO glass surface, TiO2The protrusion on nano-rod film surface is by thinner nanometer rods The TiO of composition2Spike cluster, these TiO2Spike cluster is higher than TiO2Nanometer stick array constitutes dysmorphism, by high and low Laminated film.Fig. 2 b is ultra-thin g-C obtained by embodiment one3N4The TiO of covering2The SEM of dysmorphism array film sample shines Piece.It can be seen that TiO from Fig. 2 b photo2Nanometer stick array and spike cluster dysmorphism nano-structure array film surface quilt The g-C of ultra-thin curling3N4Covering is in version transparence, obtains ultra-thin g-C3N4The TiO of covering2Dysmorphism array film.
Fig. 3 is ultra-thin g-C obtained by embodiment one3N4The TiO of covering2Dysmorphism array film sample is used for photoelectricity The UV-Vis absorption spectrum of rhodamine B in catalytic degradation aqueous solution.As can be seen that after reaction carries out 60min, rhodamine in solution The degradation rate of B has been approached 100%, this illustrates g-C3N4The TiO of covering2Dysmorphism array film electrode is suitable for aqueous solution The photoelectrocatalysis efficient degradation of rhodamine B.
By ultra-thin g-C obtained by embodiment one3N4The TiO of covering2Dysmorphism array film is used for water as optoelectronic pole Photoelectrocatalysis decomposing hydrogen-production, the experimental results showed that, since relative to Ag/AgCl electrode bias -0.3V, with the liter of voltage Height, the density of photocurrent that optoelectronic pole generates increase sharply, and when relative to Ag/AgCl electrode bias 0.2V, density of photocurrent is Up to 1.1mA/cm2.Since density of photocurrent is higher, the efficiency of optical electro-chemistry hydrogen production by water decomposition gas is higher, photoelectrochemical behaviour Also better, therefore ultra-thin g-C3N4The TiO of covering2Dysmorphism array film has excellent photoelectrocatalysis as optoelectronic pole Hydrogen production by water decomposition performance.The big reason of the electrode saturation photocurrent is the large area g-C due to preparation3N4Ultra-thin curling nanometer sheet Be conducive to improve the utilization rate of visible light, while improving the transmitance to ultraviolet light, it is ensured that TiO2Ultraviolet light is made full use of, and The large area g-C of preparation3N4Ultra-thin curling nanometer sheet increases and TiO2Nanometer rods and spike cluster dysmorphism are staggered Contact area is conducive to the separative efficiency for improving photo-generated carrier, to improve density of photocurrent.
G-C obtained prepared by the present invention3N4/TiO2Both there is film photoelectric catalysis material high photoelectrocatalysis to decompose water Hydrogen production efficiency, while there is good PhotoelectrocatalytiPerformance Performance to the degradation of organic dyestuff in water.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation is equivalent without departing from other any changes made under the principle of the present invention and technical process, substitution, simplified etc. Displacement, should all be included within protection scope of the present invention.

Claims (1)

1. a kind of ultra-thin g-C3N4The TiO of covering2Dysmorphism array film and preparation method thereof, which is characterized in that the film By ultra-thin curling g-C3N4The rutile TiO of covering2Nanometer stick array and spike cluster dysmorphism array nanostructure structure At preparation method includes the following steps：
(1) pretreatment of FTO glass：By FTO glass-cutting at specification be 1cm × 2.5cm small pieces, then it is successively immersed in Acetone, dehydrated alcohol, in deionized water, ultrasound 2-5min respectively, after sufficiently cleaning up, in 70 DEG C of dry 2h；
(2)TiO2The preparation of nanometer rods and spike cluster dysmorphism array：The titanium sulfate of 0.2-0.3g is dissolved in deionized water In, 4-8ml concentrated hydrochloric acid is then added, is made into the mixed solution of 20ml homogeneous transparent；Mixed solution is transferred to polytetrafluoro In the autoclave of ethylene liner, then in the solution by the pretreated two panels FTO glass opposed vertical placement of step (1), so Autoclave is sealed afterwards, heats 1-12h at 120-200 DEG C；After reaction, it by autoclave cooled to room temperature, takes out FTO glass is successively cleaned three times with deionized water and ethyl alcohol, in 70 DEG C of dry 2h；Dry FTO glass is finally put into tubular type In furnace, it is warming up to 500-600 DEG C with the heating rate of 1-10 DEG C/min, 1-4h is kept the temperature, obtains TiO2Nanometer rods and spike cluster Dysmorphism array film；
(3) TiO will be loaded2The FTO electro-conductive glass of dysmorphism array film is placed in reaction tank, and reaction tank is put into container, 100-500mg melamine (urea or dicyandiamide) is taken to be put into container, it is closed, it places into tube furnace with 2-10 DEG C/min's Speed is raised to 500 DEG C -600 DEG C, keeps the temperature 1-4h.
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