CN104692466A - Non-template method for preparing alpha-Fe2O3 hollow tubular nano film - Google Patents

Non-template method for preparing alpha-Fe2O3 hollow tubular nano film Download PDF

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CN104692466A
CN104692466A CN201510044711.3A CN201510044711A CN104692466A CN 104692466 A CN104692466 A CN 104692466A CN 201510044711 A CN201510044711 A CN 201510044711A CN 104692466 A CN104692466 A CN 104692466A
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film
conductive substrates
hollow tubular
fe2o3
putting
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CN104692466B (en
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焦吉庆
唐建国
王瑶
杨化森
刘继宪
黄林军
劳伦斯·A·巴菲奥
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Qingdao University
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Abstract

The invention belongs to the technical field of semiconductor nano material preparation, and relates to a non-template method for preparing an alpha-Fe2O3 hollow tubular nano film, which comprises the following steps: respectively adding iron chloride, sodium nitrate and sodium fluoride into a beaker, adding distilled water, stirring to prepare a homogeneous solution, transferring into a teflon-lined reactor, putting a clean conducting substrate into the teflon-lined reactor, sealing, transferring into a high-pressure reaction kettle, putting into a drying oven, reacting, taking out the high-pressure reaction kettle, naturally cooling to room temperature, taking out the conducting substrate, washing with distilled water, airing, putting the conducting substrate containing an alpha-Fe2O3 precursor film into a porcelain boat, putting into a muffle furnace, heating and keeping the temperature; and finally, taking out the porcelain boat, and naturally cooling to obtain the alpha-Fe2O3 hollow tubular nano film on the conducting substrate. The preparation method is simple and scientific in principle; and the prepared nano film has the advantages of high stability and wide application range.

Description

A kind of non-template prepares α-Fe 2o 3the method of hollow tubular nano thin-film
Technical field:
The invention belongs to semiconductor nano material preparing technical field, relate to a kind of preparation method of nano thin-film of hollow tubular structure, particularly a kind of non-template prepares α-Fe 2o 3the method of hollow tubular nano thin-film.
Background technology:
Since E.Becquerel in 1839 finds the photovoltaic effect of semi-conductor, utilize nearly decades the photovoltaic effect of semi-conductor to make sunlight be converted to electric energy and chemical energy, caused the extensive concern of investigator.In numerous semiconductor material, titanium dioxide (TiO 2) as standard material, in photochemistry, obtain investigation and application widely.But, TiO 2band gap be 3.2eV, the ultraviolet part in sunlight can only be absorbed, greatly reduce the specific absorption of sunlight, cause the utilization ratio of sun power and transformation efficiency to reduce.Therefore, increasing semiconductor nano material is widely studied, wherein Indian red (rhombohedral iron ore, α-Fe 2o 3) 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 assimilated efficiency of visible region; Suitable conduction band and valence band location make it as photocatalytic water material; In addition, its stable chemical nature, storage capacity is enriched, cheap and easy to get, other semi-conductors relatively, Indian red (rhombohedral iron ore, α-Fe 2o 3) in photovoltaic applications, have more advantage, as aspects such as solar cell, photogalvanic cell and photocatalytic water.But, Indian red (rhombohedral iron ore, α-Fe 2o 3) material itself also also exists easily lower under compound, the room temperature hole mobility (0.01cm of diffusion length short (2-4 nanometer) of the easy compound of light induced electron and hole, current carrier 2v -1s -1), there is the shortcomings such as certain overpotential, these shortcomings make α-Fe 2o 3application be limited by very large.
At present, to α-Fe 2o 3method of modifying have a variety of, be generally divided into two classes: one is the crystalline structure being improved material by element doping; Two is to α-Fe 2o 3carry out the regulation and control of the aspect such as size, form, effectively improved the photoelectric property of material by modification.To first method, investigator successful by element dopings such as Co, Pt, Ni, Ti and Si in α-Fe 2o 3among lattice, research finds, by the doping of xenogenesis element, effectively can increase the rate of migration of current carrier, improve photolytic activity; But most active absorption layer is in the crystal of semi-conductor-solution surface to 10 nanometer, in addition, effectively can reach the surface of semiconductor material at the current carrier of this thickness, reduce the probability of its compound.Therefore, controlling certain thickness and size is key to rhombohedral iron ore morphology control.In numerous structural form, the nanostructure of hollow, as nanotube, nanometer ball and other forms, successively be produced out, relative to other nano shape, the nano wall structure that hollow structure is thin can effectively improve its photolytic activity, shows good photoelectric transformation efficiency.
At present, hollow structure nanometer α-Fe is prepared in prior art 2o 3method comprise template, self-assembly method and electrochemical oxidation process etc., wherein, template is the most direct method, and wherein a kind of method utilizes zinc oxide (ZnO) as Template preparation hollow α-Fe 2o 3but its nanometer wall thickness prepared has exceeded 10 nanometers, need in subsequent process to remove template; Another kind of preparation method, first synthesizes nano carbon microsphere or other organic compound nanometer balls of certain size, then wraps up it, finally obtain having certain thickness α-Fe 2o 3hollow 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 prepares certain thickness α-Fe by controlling certain voltage and current density 2o 3nanotube, but can not form hollow structure, 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-Fe 2o 3the method of hollow tubular nano thin-film, adopts simple synthetic route, does not use any template, at the upper α-Fe utilizing vertically arrangement of conductive glass (FTO) 2o 3the nanotube-shaped material of hollow.
Summary of the invention:
The object of the invention is to the shortcoming overcoming prior art existence, seek design one and do not use any template, conductive glass is prepared α-Fe 2o 3the method of the simple possible of hollow tubular nano thin-film, first by preparing persursor material to the selection of different additive and control, then heat-treat, finally synthesizing tube wall is 10 nanometers, at the α-Fe that FTO conductive glass surface vertically arranges 2o 3hollow tubular nano thin-film.
To achieve these goals, preparation technology of the present invention comprises the following steps:
(1), first cut lengths are the FTO conductive glass of 2cm × 2cm, naturally dry, the conductive substrates of formation cleaning to FTO conductive glass after adopting prior art to carry out ultrasonic cleaning with washing composition, deionized water, acetone, deionized water and different alcohol successively;
(2), by 0.324g iron(ic) chloride, 0.170g SODIUMNITRATE and 0.016g Sodium Fluoride add beaker respectively, then add 20ml distilled water be mixed with homogeneous solution under the stirring of magnetic stirrer;
(3), the homogeneous solution that step (2) obtains is proceeded in polytetrafluoroethylliner liner reactor;
(4) face up, again by the conductive substrates of cleaning and put into polytetrafluoroethylliner liner reactor, then the sealing of polytetrafluoroethylliner liner reactor is transferred in autoclave, and put into baking oven and react 6 hours under 95 DEG C of conditions;
(5), by autoclave take 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-Fe 2o 3the conductive substrates of precursor film;
(6), will containing α-Fe 2o 3put into retort furnace again after the conductive substrates of precursor film puts into porcelain boat, with the ramp of per minute 5 DEG C, be heated to 550 DEG C in atmosphere, be incubated 2 hours;
(7), finally taken out by porcelain boat, naturally cooling in atmosphere, conductive substrates prepares scarlet, vertically disposed α-Fe 2o 3hollow tubular nano thin-film.
The present invention compared with prior art, adopts simple synthetic route, does not use any template, and conductive glass (FTO) has synthesized the α-Fe of vertical arrangement 2o 3the nanotube-shaped nano thin-film of hollow, its preparation method is simple, and scientific in principle, the nano thin-film stability of preparation is high, is widely used, and has potential application prospect at numerous areas such as photochemical catalysis, inorganic solar cell and photocatalytic water.
Accompanying drawing illustrates:
Fig. 1 is α-Fe described in the embodiment of the present invention 1 2o 3precursor film (left figure) and α-Fe 2o 3the electronic photo of hollow tubular nano thin-film (right figure).
α-Fe prepared by Fig. 2 the present invention 2o 3transmission electron microscope (TEM) photo of hollow tubular nano thin-film, illustration shows its thickness of pipe and is approximately 10 nanometers.
Fig. 3 is α-Fe prepared by the present invention 2o 3precursor film and α-Fe 2o 3the X-ray diffractogram of hollow tubular nano thin-film (in figure 2), wherein 1 is α-Fe 2o 3precursor film (sample before pyroprocessing), 2 is α-Fe 2o 3(the sample) ， ﹟ after pyroprocessing represents the SnO on FTO surface to hollow tubular nano thin-film 2diffraction peak, ◆ represent the α-Fe generated 2o 3diffraction peak.
Fig. 4 is the X-ray energy spectrum figure (EDX) of Sn, Fe and O element that the present invention relates to.
Fig. 5 is α-Fe prepared by the embodiment of the present invention 4 2o 3transmission electron microscope (TEM) photo of powder.
Embodiment:
Below by specific embodiment, and the present invention is further elaborated by reference to the accompanying drawings.
Embodiment 1:
The present embodiment prepares α-Fe 2o 3the concrete technology of hollow tubular nano thin-film comprises the following steps:
(1), first cut lengths are the FTO conductive glass of 2cm × 2cm, naturally dry, the conductive substrates of formation cleaning to FTO conductive glass after adopting prior art to carry out ultrasonic cleaning with washing composition, deionized water, acetone, deionized water and different alcohol successively;
(2), by 0.324g iron(ic) chloride, 0.170g SODIUMNITRATE and 0.016g Sodium Fluoride add beaker respectively, then add 20ml distilled water be mixed with homogeneous solution under the stirring of magnetic stirrer, the homogeneous solution obtained is rust, and has molecule to exist;
(3), the homogeneous solution that step (2) obtains is proceeded to rapidly in polytetrafluoroethylliner liner reactor;
(4) face up, again by the conductive substrates of cleaning and put into polytetrafluoroethylliner liner reactor, then the sealing of polytetrafluoroethylliner liner reactor is transferred in autoclave, and put into baking oven and react 6 hours under 95 DEG C of conditions;
(5), by autoclave take 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-Fe 2o 3the conductive substrates of precursor film; Can see conductive substrates there is faint yellow film by the left figure of Fig. 1;
(6), will containing α-Fe 2o 3put into retort furnace again after the conductive substrates of precursor film puts into porcelain boat, with the ramp of per minute 5 DEG C, be heated to 550 DEG C in atmosphere, be incubated 2 hours;
(7), finally taken out by porcelain boat, naturally cooling in atmosphere, namely prepares the vertically disposed α of scarlet-Fe in conductive substrates 2o 3hollow tubular nano thin-film, shown in figure as right in Fig. 1.
α-Fe prepared by the present embodiment 2o 3hollow tubular nanometer thin film transmission electron microscope (TEM) photo as shown in Figure 2, as can be seen from Figure, α-Fe 2o 3the thickness of pipe 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, add in the homogeneous solution only obtained in step (2) and slowly drip 10 milliliters, the dilute hydrochloric acid that weight percent concentration is 10%, to dissolve the precipitation produced, its concrete steps are as follows:
(1), first cut lengths are the FTO conductive glass of 2cm × 2cm, naturally dry, the conductive substrates of formation cleaning to FTO conductive glass after adopting prior art to carry out ultrasonic cleaning with washing composition, deionized water, acetone, deionized water and different alcohol successively;
(2), by 0.324g iron(ic) chloride, 0.170g SODIUMNITRATE and 0.016g Sodium Fluoride add beaker respectively, then add 20ml distilled water be mixed with homogeneous solution under the stirring of magnetic stirrer, the homogeneous solution obtained is rust, and has molecule to exist; Then slowly drip 10 milliliters, the dilute hydrochloric acid of 10%, make resolution of precipitate;
(3), the homogeneous solution that step (2) obtains is proceeded to rapidly in polytetrafluoroethylliner liner reactor;
(4) face up, again by the conductive substrates of cleaning and put into polytetrafluoroethylliner liner reactor, then the sealing of polytetrafluoroethylliner liner reactor is transferred in autoclave, and put into baking oven and react 6 hours under 95 DEG C of conditions;
(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 does not form any material, this can not generate α-Fe on the surface of FTO conductive glass after illustrating and adding dilute hydrochloric acid 2o 3precursor film.
Embodiment 3:
The present embodiment only carries out step (1)-(5) of embodiment 1, and no longer carry out pyroprocessing, detailed process is:
(1), first cut lengths are the FTO conductive glass of 2cm × 2cm, naturally dry, the conductive substrates of formation cleaning to FTO conductive glass after adopting prior art to carry out ultrasonic cleaning with washing composition, deionized water, acetone, deionized water and different alcohol successively;
(2), by 0.324g iron(ic) chloride, 0.170g SODIUMNITRATE and 0.016g Sodium Fluoride add beaker respectively, then add 20ml distilled water be mixed with homogeneous solution under the stirring of magnetic stirrer, the homogeneous solution obtained is rust, and has molecule to exist;
(3), the homogeneous solution that step (2) obtains is proceeded to rapidly in polytetrafluoroethylliner liner reactor;
(4) face up, again by the conductive substrates of cleaning and put into polytetrafluoroethylliner liner reactor, then the sealing of polytetrafluoroethylliner liner reactor is transferred in autoclave, and put into baking oven and react 6 hours under 95 DEG C of conditions;
(5), by autoclave take out from baking oven, after naturally cooling to room temperature, open autoclave tweezers and take out conductive substrates, with distilled water wash, dry, at the lurid film of Surface Creation one deck of conductive substrates, through XRD analysis, its surface does not generate α-Fe 2o 3hollow tubular nano thin-film.
Embodiment 4:
The present embodiment does not generate α-Fe at FTO conductive glass surface 2o 3nano thin-film, other steps are identical with embodiment step (2)-(7), and detailed process is
(1), by 0.324g iron(ic) chloride, 0.170g SODIUMNITRATE and 0.016g Sodium Fluoride add beaker respectively, then add 20ml distilled water be mixed with homogeneous solution under the stirring of magnetic stirrer, the homogeneous solution obtained is rust, and has molecule to exist;
(2), the homogeneous solution that step (2) obtains is proceeded to rapidly in polytetrafluoroethylliner liner reactor;
(3) face up, again by the conductive substrates of cleaning and put into polytetrafluoroethylliner liner reactor, then the sealing of polytetrafluoroethylliner liner reactor is transferred in autoclave, and put into baking oven and react 6 hours under 95 DEG C of conditions;
(4), by autoclave take out from baking oven, after naturally cooling to room temperature, obtain α-Fe 2o 3precursor powder, by α-Fe 2o 3precursor powder uses 5 ml waters and ethanol respectively, respectively wash three times for subsequent use;
(5), by α-Fe prepared by step (4) 2o 3precursor powder puts into porcelain boat, puts into retort furnace in the lump, with the ramp of per minute 5 DEG C, is heated to 550 DEG C in atmosphere, is incubated 2 hours;
(6), by porcelain boat take out, naturally cooling in atmosphere, can be observed to generate red α-Fe 2o 3powder, as shown in Figure 5; Through test, do not having FTO conductive glass to deposit in case, its sample cluster more severe, the form of sample does not present the nanostructure of hollow yet.

Claims (1)

1. a non-template prepares α-Fe 2o 3the method of hollow tubular nano thin-film, is characterized in that preparation technology comprises the following steps:
(1), first cut lengths are the FTO conductive glass of 2cm × 2cm, naturally dry, the conductive substrates of formation cleaning to FTO conductive glass after adopting prior art to carry out ultrasonic cleaning with washing composition, deionized water, acetone, deionized water and different alcohol successively;
(2), by 0.324g iron(ic) chloride, 0.170g SODIUMNITRATE and 0.016g Sodium Fluoride add beaker respectively, then add 20ml distilled water be mixed with homogeneous solution under the stirring of magnetic stirrer;
(3), the homogeneous solution that step (2) obtains is proceeded in polytetrafluoroethylliner liner reactor;
(4) face up, again by the conductive substrates of cleaning and put into polytetrafluoroethylliner liner reactor, then the sealing of polytetrafluoroethylliner liner reactor is transferred in autoclave, and put into baking oven and react 6 hours under 95 DEG C of conditions;
(5), by autoclave take 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-Fe 2o 3the conductive substrates of precursor film;
(6), will containing α-Fe 2o 3put into retort furnace again after the conductive substrates of precursor film puts into porcelain boat, with the ramp of per minute 5 DEG C, be heated to 550 DEG C in atmosphere, be incubated 2 hours;
(7), finally taken out by porcelain boat, naturally cooling in atmosphere, conductive substrates prepares scarlet, vertically disposed α-Fe 2o 3hollow tubular nano thin-film.
CN201510044711.3A 2015-01-29 2015-01-29 A kind of non-template prepares α-Fe2o3the method of hollow tubular nano thin-film Expired - Fee Related CN104692466B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105220221A (en) * 2015-11-12 2016-01-06 华东理工大学 A kind of preparation method of mesoporous single crystals ferric oxide and photoelectrochemistry water splitting device thereof
CN106006756A (en) * 2016-05-19 2016-10-12 青岛大学 Method for manufacturing Fe2O3 nanometer film curled tubes

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
H.K. MULMUDI等: "Controlled growth of hematite (α-Fe2O3) nanorod array on fluorine doped tin oxide:Synthesis and photoelectrochemical properties", 《ELECTROCHEMISTRY COMMUNICATIONS》, 15 June 2011 (2011-06-15), pages 951 - 954 *
LINLIN PENG等: "Surface photovoltage characterization of an oriented α-Fe2O3 nanorod array", 《CHEMICAL PHYSICS LETTERS》, 20 May 2008 (2008-05-20), pages 159 - 163 *
刘甲甲等: "α-Fe2O3纳米管制备方法的研究进展", 《功能材料》, vol. 45, no. 9, 31 December 2014 (2014-12-31), pages 9001 - 9007 *
台玉萍等: "单晶态α-Fe2O3纳米管的制备及其形成机理探讨", 《河北化工》, vol. 32, no. 10, 31 October 2009 (2009-10-31) *
叶芸等: "Fe2O3微纳米管阵列的制备及场发射性能研究", 《功能材料》, vol. 44, no. 5, 31 December 2013 (2013-12-31), pages 673 - 676 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105220221A (en) * 2015-11-12 2016-01-06 华东理工大学 A kind of preparation method of mesoporous single crystals ferric oxide and photoelectrochemistry water splitting device thereof
CN105220221B (en) * 2015-11-12 2018-06-19 华东理工大学 A kind of preparation method of mesoporous single crystals iron oxide and its optical electro-chemistry water splitting device
CN106006756A (en) * 2016-05-19 2016-10-12 青岛大学 Method for manufacturing Fe2O3 nanometer film curled tubes

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