CN104692466B - A kind of non-template prepares α-Fe2o3the method of hollow tubular nano thin-film - Google Patents
A kind of non-template prepares α-Fe2o3the method of hollow tubular nano thin-film Download PDFInfo
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- CN104692466B CN104692466B CN201510044711.3A CN201510044711A CN104692466B CN 104692466 B CN104692466 B CN 104692466B CN 201510044711 A CN201510044711 A CN 201510044711A CN 104692466 B CN104692466 B CN 104692466B
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Abstract
The invention belongs to semiconductor nano material preparing technical field, relate to a kind of non-template and prepare α Fe2O3The method of hollow tubular nano thin-film, first iron chloride, sodium nitrate and sodium fluoride are separately added into beaker, adding after distilled water stirring is configured to homogeneous solution proceeds in polytetrafluoroethylliner liner reactor, putting into seal after in polytetrafluoroethylliner liner reactor by clean conductive substrates again transfers in autoclave, and after putting in baking oven reaction, autoclave is taken out, naturally cool to take out after room temperature conductive substrates, with distilled water wash, dry, then obtain containing α Fe2O3The conductive substrates of precursor film places into heating and thermal insulation in Muffle furnace after putting into porcelain boat；Finally porcelain boat is taken out, natural cooling, conductive substrates prepares α Fe2O3Hollow tubular nano thin-film；Its preparation method is simple, scientific in principle, and the nano thin-film stability of preparation is high, is widely used.
Description
Technical field:
The invention belongs to semiconductor nano material preparing technical field, relate to the preparation method of the nano thin-film of a kind of hollow tubular structure, particularly a kind of non-template prepares α-Fe2O3The method of hollow tubular nano thin-film.
Background technology:
Since E.Becquerel in 1839 finds the photoelectric effect of quasiconductor, recent decades utilizes the photoelectric effect of quasiconductor to make sunlight be converted to electric energy and chemical energy, causes the extensive concern of researcher.In numerous semi-conducting materials, titanium dioxide (TiO2) as standard material, studied widely in terms of photochemistry and apply.But, TiO2Band gap be 3.2eV, the ultraviolet part in sunlight can only be absorbed, greatly reduce the absorbance of sunlight, cause the utilization rate of solar energy and transformation efficiency to reduce.Therefore, increasing semiconductor nano material is widely studied, wherein ferric oxide (bloodstone, α-Fe2O3) there is suitable band gap (2.2eV), this energy level can absorb the visible light part in sunlight, widens the absorption region of light, increases the absorption efficiency of visible region；Suitably conduction band and valence band location makes it as photocatalytic water material；Additionally, its stable chemical nature, storage capacity is enriched, cheap and easy to get, other quasiconductors relatively, ferric oxide (bloodstone, α-Fe2O3) more advantage in terms of photovoltaic applications, in terms of solaode, photochemical cell and photocatalytic water etc..But, ferric oxide (bloodstone, α-Fe2O3) material itself there is also that light induced electron and hole easily diffusion length short (2-4 nanometer) compound, carrier is the most compound, hole mobility (0.01cm relatively low under room temperature2V-1s-1), there is the shortcomings such as certain overpotential, these shortcomings make α-Fe2O3Application be limited by very large.
At present, to α-Fe2O3Method of modifying have a variety of, be generally divided into two classes: one is the crystal structure being improved material by element doping；Two is to α-Fe2O3Carry out the regulation and control of the aspect such as size, form, be effectively improved the photoelectric property of material by modification.To first method, researcher successfully by element dopings such as Co, Pt, Ni, Ti and Si in α-Fe2O3Among lattice, research finds, by the doping of xenogenesis element, can effectively increase the migration rate of carrier, improve photolytic activity；But most active absorbed layer is in the crystal of quasiconductor-solution surface to 10 nanometers, additionally, the surface of semi-conducting material can be effectively accomplished at the carrier of this thickness, reduce its compound probability.Therefore, control certain thickness and size is the key to bloodstone morphology control.In numerous configurations, the nanostructured of hollow, such as nanotube, nanosphere and other forms, successively it is prepared out, relative to other nano shape, the nano wall structure that hollow structure is thin can be effectively improved its photolytic activity, it is shown that preferably photoelectric transformation efficiency.
At present, prior art is prepared hollow structure nanometer α-Fe2O3Method include template, self-assembly method and electrochemical oxidation process etc., wherein, template is most straightforward approach, and one of which method is to utilize zinc oxide (ZnO) to prepare hollow α-Fe as template2O3, but the nanometer wall thickness that it is prepared has exceeded 10 nanometers, needs removing template in subsequent process；Another kind of preparation method, first synthesizes nano carbon microsphere or other organic compound nanospheres of certain size, then wraps up it, finally obtain and have certain thickness α-Fe2O3Hollow nanospheres, the method preparation method is simple, but needs high-temperature calcination, and the material crystalline of synthesis is poor, affects photoelectric transformation efficiency.Electrochemical method is to prepare certain thickness α-Fe by the certain voltage and current density of control2O3Nanotube, but hollow structure can not be formed, the crystallinity of its nano material is poor, and can affect the chemical stability of material.Therefore, seek a kind of non-template and prepare α-Fe2O3The method of hollow tubular nano thin-film, uses simple synthetic route, does not use any template, above utilizes the α-Fe being vertically arranged at electro-conductive glass (FTO)2O3The nanotube-shaped material of hollow.
Summary of the invention:
It is an object of the invention to the shortcoming overcoming prior art to exist, seek to design one and do not use any template, electro-conductive glass is prepared α-Fe2O3The method of the simple possible of hollow tubular nano thin-film, first passes through the selection to different additive and prepares persursor material with control, then carry out heat treatment, and finally synthesizing tube wall is 10 nanometers, at the α-Fe that FTO conductive glass surface is vertically arranged2O3Hollow tubular nano thin-film.
To achieve these goals, the preparation technology of the present invention comprises the following steps:
(1), first cut lengths be the FTO electro-conductive glass of 2cm × 2cm, FTO electro-conductive glass uses prior art naturally dry after carrying out ultrasonic cleaning with detergent, deionized water, acetone, deionized water and different alcohol successively, forms the conductive substrates of cleaning；
(2), 0.324g iron chloride, 0.170g sodium nitrate and 0.016g sodium fluoride are separately added into beaker, add 20ml distilled water and be configured to homogeneous solution under the stirring of magnetic stirrer；
(3), the homogeneous solution that step (2) obtains is proceeded in polytetrafluoroethylliner liner reactor；
(4) facing up, again by clean conductive substrates puts in polytetrafluoroethylliner liner reactor, is then sealed by polytetrafluoroethylliner liner reactor and transfers in autoclave, and puts in baking oven and react 6 hours under the conditions of 95 DEG C；
(5), autoclave is taken out from baking oven, after naturally cooling to room temperature, open autoclave tweezers and take out conductive substrates, with distilled water wash, dry, obtain containing α-Fe2O3The conductive substrates of precursor film；
(6), will be containing α-Fe2O3The conductive substrates of precursor film places in Muffle furnace after putting into porcelain boat, with the ramp of 5 DEG C per minute, is heated to 550 DEG C in atmosphere, is incubated 2 hours；
(7), finally by porcelain boat take out, natural cooling in atmosphere, conductive substrates prepares peony, vertically disposed α-Fe2O3Hollow tubular nano thin-film.
The present invention compared with prior art, uses simple synthetic route, does not use any template, has synthesized the α-Fe being vertically arranged on electro-conductive glass (FTO)2O3The nanotube-shaped nano thin-film of hollow, its preparation method is simple, scientific in principle, and the nano thin-film stability of preparation is high, is widely used, has potential application prospect at numerous areas such as photocatalysis, inorganic solar cell and photocatalytic water.
Accompanying drawing illustrates:
Fig. 1 is α-Fe described in the embodiment of the present invention 12O3Precursor film (left figure) and α-Fe2O3The electronic photo of hollow tubular nano thin-film (right figure).
α-Fe prepared by Fig. 2 present invention2O3Transmission electron microscope (TEM) photo of hollow tubular nano thin-film, illustration shows that its pipe thickness is about 10 nanometers.
Fig. 3 is α-Fe prepared by the present invention2O3Precursor film and α-Fe2O3The X-ray diffractogram of hollow tubular nano thin-film (in figure 2), wherein 1 is α-Fe2O3Precursor film (sample before high-temperature process), 2 is α-Fe2O3Hollow tubular nano thin-film (sample after high-temperature process), represents the SnO on FTO surface2Diffraction maximum, ◆ represent the α-Fe generated2O3Diffraction maximum.
Fig. 4 is the X-ray energy spectrogram (EDX) of Sn, Fe and O element that the present invention relates to.
Fig. 5 is the α-Fe of the embodiment of the present invention 4 preparation2O3Transmission electron microscope (TEM) photo of powder.
Detailed description of the invention:
Below by specific embodiment, and the present invention is further elaborated to combine accompanying drawing.
Embodiment 1:
The present embodiment prepares α-Fe2O3The concrete technology of hollow tubular nano thin-film comprises the following steps:
(1), first cut lengths be the FTO electro-conductive glass of 2cm × 2cm, FTO electro-conductive glass uses prior art naturally dry after carrying out ultrasonic cleaning with detergent, deionized water, acetone, deionized water and different alcohol successively, forms the conductive substrates of cleaning；
(2), 0.324g iron chloride, 0.170g sodium nitrate and 0.016g sodium fluoride being separately added into beaker, add 20ml distilled water and be configured to homogeneous solution under the stirring of magnetic stirrer, the homogeneous solution obtained is rust, and with the presence of molecule；
(3), the homogeneous solution that step (2) obtains is proceeded to rapidly in polytetrafluoroethylliner liner reactor；
(4) facing up, again by clean conductive substrates puts in polytetrafluoroethylliner liner reactor, is then sealed by polytetrafluoroethylliner liner reactor and transfers in autoclave, and puts in baking oven and react 6 hours under the conditions of 95 DEG C；
(5), autoclave is taken out from baking oven, after naturally cooling to room temperature, open autoclave tweezers and take out conductive substrates, with distilled water wash, dry, obtain containing α-Fe2O3The conductive substrates of precursor film；By the left figure of Fig. 1 it will be seen that there is faint yellow thin film in conductive substrates；
(6), will be containing α-Fe2O3The conductive substrates of precursor film places in Muffle furnace after putting into porcelain boat, with the ramp of 5 DEG C per minute, is heated to 550 DEG C in atmosphere, is incubated 2 hours；
(7), finally by porcelain boat take out, natural cooling in atmosphere, in conductive substrates, i.e. prepare peony vertically disposed α-Fe2O3Hollow tubular nano thin-film, shown in figure as right in Fig. 1.
α-Fe prepared by the present embodiment2O3Hollow tubular nanometer thin film transmission electron microscope (TEM) photo as in figure 2 it is shown, as can be seen from Figure, α-Fe2O3The pipe thickness of hollow tubular nano thin-film is less than 10 nanometers.
Embodiment 2:
The present embodiment is identical with step (1)-(5) in embodiment 1, in the homogeneous solution that step (2) obtains, only add the dilute hydrochloric acid 10 milliliters that slowly dropping weight percent concentration is 10%, to dissolve the precipitation produced, it specifically comprises the following steps that
(1), first cut lengths be the FTO electro-conductive glass of 2cm × 2cm, FTO electro-conductive glass uses prior art naturally dry after carrying out ultrasonic cleaning with detergent, deionized water, acetone, deionized water and different alcohol successively, forms the conductive substrates of cleaning；
(2), 0.324g iron chloride, 0.170g sodium nitrate and 0.016g sodium fluoride being separately added into beaker, add 20ml distilled water and be configured to homogeneous solution under the stirring of magnetic stirrer, the homogeneous solution obtained is rust, and with the presence of molecule；The most slowly the dilute hydrochloric acid 10 milliliters of dropping 10%, makes resolution of precipitate；
(3), the homogeneous solution that step (2) obtains is proceeded to rapidly in polytetrafluoroethylliner liner reactor；
(4) facing up, again by clean conductive substrates puts in polytetrafluoroethylliner liner reactor, is then sealed by polytetrafluoroethylliner liner reactor and transfers in autoclave, and puts in baking oven and react 6 hours under the conditions of 95 DEG C；
(5), autoclave is taken out from baking oven, after naturally cooling to room temperature, open autoclave tweezers and take out conductive substrates, with distilled water wash, dry, conductive substrates is formed without any material, after this explanation adds dilute hydrochloric acid, α-Fe can not be generated on the surface of FTO electro-conductive glass2O3Precursor film.
Embodiment 3:
The present embodiment only carries out step (1)-(5) of embodiment 1, no longer carries out high-temperature process, and detailed process is:
(1), first cut lengths be the FTO electro-conductive glass of 2cm × 2cm, FTO electro-conductive glass uses prior art naturally dry after carrying out ultrasonic cleaning with detergent, deionized water, acetone, deionized water and different alcohol successively, forms the conductive substrates of cleaning；
(2), 0.324g iron chloride, 0.170g sodium nitrate and 0.016g sodium fluoride being separately added into beaker, add 20ml distilled water and be configured to homogeneous solution under the stirring of magnetic stirrer, the homogeneous solution obtained is rust, and with the presence of molecule；
(3), the homogeneous solution that step (2) obtains is proceeded to rapidly in polytetrafluoroethylliner liner reactor；
(4) facing up, again by clean conductive substrates puts in polytetrafluoroethylliner liner reactor, is then sealed by polytetrafluoroethylliner liner reactor and transfers in autoclave, and puts in baking oven and react 6 hours under the conditions of 95 DEG C；
(5), autoclave is taken out from baking oven, after naturally cooling to room temperature, open autoclave tweezers and take out conductive substrates, with distilled water wash, dry, at one layer of lurid thin film of Surface Creation of conductive substrates, through XRD analysis, its surface does not generate α-Fe2O3Hollow tubular nano thin-film.
Embodiment 4:
The present embodiment does not generates α-Fe at FTO conductive glass surface2O3Nano thin-film, other steps are identical with embodiment step (2)-(7), and detailed process is
(1), 0.324g iron chloride, 0.170g sodium nitrate and 0.016g sodium fluoride being separately added into beaker, add 20ml distilled water and be configured to homogeneous solution under the stirring of magnetic stirrer, the homogeneous solution obtained is rust, and with the presence of molecule；
(2), the homogeneous solution that step (2) obtains is proceeded to rapidly in polytetrafluoroethylliner liner reactor；
(3) facing up, again by clean conductive substrates puts in polytetrafluoroethylliner liner reactor, is then sealed by polytetrafluoroethylliner liner reactor and transfers in autoclave, and puts in baking oven and react 6 hours under the conditions of 95 DEG C；
(4), autoclave is taken out from baking oven, after naturally cooling to room temperature, obtain α-Fe2O3Precursor powder, by α-Fe2O3Precursor powder respectively with 5 milliliters of water and ethanol, respectively wash three times standby；
(5), α-Fe prepared by step (4)2O3Precursor powder is put in porcelain boat, puts in Muffle furnace in the lump, with the ramp of 5 DEG C per minute, is heated to 550 DEG C in atmosphere, is incubated 2 hours；
(6), porcelain boat is taken out, natural cooling in atmosphere, can be observed to generate the α-Fe of redness2O3Powder, as shown in Figure 5；Through test, in the presence of not having FTO electro-conductive glass, the comparison of its sample cluster is severe, and the form of sample does not the most present the nanostructured of hollow.
Claims (1)
1. a non-template prepares α-Fe2O3The method of hollow tubular nano thin-film, it is characterised in that preparation work
Skill comprises the following steps:
(1), first cut lengths be the FTO electro-conductive glass of 2cm × 2cm, FTO electro-conductive glass is used existing
Technology is had naturally to dry in the air after carrying out ultrasonic cleaning with detergent, deionized water, acetone, deionized water and different alcohol successively
Dry, form clean conductive substrates；
(2), 0.324g iron chloride, 0.170g sodium nitrate and 0.016g sodium fluoride are separately added into beaker, then
Add 20ml distilled water and be configured to homogeneous solution under the stirring of magnetic stirrer；
(3), the homogeneous solution that step (2) obtains is proceeded in polytetrafluoroethylliner liner reactor；
(4), cleaner conductive substrates is faced up and put in polytetrafluoroethylliner liner reactor, then
Polytetrafluoroethylliner liner reactor is sealed and transfers in autoclave, and put in baking oven 95 DEG C of conditions
Lower reaction 6 hours；
(5), autoclave is taken out from baking oven, after naturally cooling to room temperature, open autoclave
Take out conductive substrates with tweezers, with distilled water wash, dry, obtain containing α-Fe2O3The conduction of precursor film
Substrate；
(6), will be containing α-Fe2O3The conductive substrates of precursor film places in Muffle furnace after putting into porcelain boat,
With the ramp of 5 DEG C per minute, it is heated to 550 DEG C in atmosphere, is incubated 2 hours；
(7), finally by porcelain boat take out, natural cooling in atmosphere, conductive substrates prepares dark red
Color, vertically disposed α-Fe2O3Hollow tubular nano thin-film.
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| CN104282847A (en) * | 2014-09-05 | 2015-01-14 | 石家庄铁道大学 | Interruptible perovskite type organic halide thin-film solar cell photo-anode preparing method |
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| CN104282847A (en) * | 2014-09-05 | 2015-01-14 | 石家庄铁道大学 | Interruptible perovskite type organic halide thin-film solar cell photo-anode preparing method |
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