CN106698523A - Preparation process of Fe2O3 nanotubes with sacrificial template method - Google Patents

Preparation process of Fe2O3 nanotubes with sacrificial template method Download PDF

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CN106698523A
CN106698523A CN201710042773.XA CN201710042773A CN106698523A CN 106698523 A CN106698523 A CN 106698523A CN 201710042773 A CN201710042773 A CN 201710042773A CN 106698523 A CN106698523 A CN 106698523A
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fto
fe2o3
nanotubes
nanotube
preparation process
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CN106698523B (en
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卢小泉
贺彩花
秦冬冬
王秋红
李洋
权晶晶
段世芳
耿园园
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Northwest Normal University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/06—Ferric oxide (Fe2O3)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/13—Nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties

Abstract

The invention discloses a preparation process of Fe2O3 nanotubes with a sacrificial template method and belongs to the technical field of preparation of a semiconductor nanomaterial. The preparation process comprises the following steps: carrying out an autocatalytic oxidation-reduction reaction on FTO glass to obtain FTO/Cu sediment; carrying out anode oxidation on the sediment to obtain FTO/Cu(OH)2 nanowires; and finally, annealing and etching the FTO/Cu(OH)2 nanowires under a nitrogen atmosphere at a high temperature, and annealing at a high temperature again to obtain the Fe2O3 nanotubes. According to the preparation process disclosed by the invention, the FTO conductive glass is used as a substrate material, CuO nanowires are used as a sacrificial template, and FeCl3.6H2O is used as an iron source to prepare the Fe2O3 nanotubes; preparation processes are simple, and experiment conditions are easy to control; in the whole preparation processes, equipment with a high price is not needed, and the cost is low; and the prepared Fe2O3 nanotubes have a very good crystal form, and the photocatalytic activity is high.

Description

Fe2O3The sacrifice template method of nanotube prepares technique
Technical field
The invention belongs to semiconductor nano material preparing technical field, and in particular to a kind of Fe2O3The sacrifice template of nanotube Method preparation technology.
Background technology
Nanometer Fe2O3It is one of study hotspot of current novel photolysis water semi-conducting material.With other photocatalytic water material phases Than Fe2O3With rich reserves, cheap, good stability and the suitable advantage of band gap width.But, nanometer Fe2O3Also deposit In numerous shortcomings, such as poorly conductive, the average free short distance in hole（About 2-4nm）Deng so as to seriously limit its photocatalytic water effect Rate, makes it in it can't put into large-scale business application at this stage.Therefore, to nanometer Fe2O3Material is modified and changed Property, photocatalysis performance higher is made it have, there is highly important Research Significance in energy field.
When semiconductor particle diameter is sufficiently small, with more preferable electricity, optics, calorifics and mechanical property.Fe2O3Nanotube Size is small so that the time that its light induced electron is diffused into surface from crystal shortens, and the probability of electronics and hole-recombination is reduced, light Solution water efficiency is improved.Susanta K. Mohapatra et al. are there is provided a kind of preparation of one-dimensional material di-iron trioxide nanotube Method (Susanta K. Mohapatra, Shiny E. John, Subarna Banerjee, and Mano Misra, Water Photooxidation by Smooth and Ultrathinr-Fe2O3 Nanotube Arrays. Chem. Mater.2009,21,3048-3055), the method be with iron as base material, be immersed in organic solvent ethylene glycol, ammonium fluoride and In water, using anodizing under conditions of voltage is 30V direct reaction 25min, so as to be obtained in situ growth of iron surface Fe2O3Nano-tube material.Though the method can well control Fe2O3The thickness of nanotube, but its maximum shortcoming is Fe2O3Nanometer Pipe deposits uneven, poor crystal form in iron surface, and higher to experiment condition requirement, and experimental cost is high.Application No. The Chinese invention patent of 201510804325.X discloses a kind of α-Fe2O3The preparation method of nanotube, by NH4、H2P4And FeCl3 Mixed aqueous solution be sufficiently stirred for, by precipitation and centrifugal separation after hydro-thermal process 48h at 220 DEG C, successively with deionized water and second Vacuum drying obtains α-Fe at 80 DEG C after alcohol cleaning2O3Nanometer monocrystalline pipe.But the method is high to equipment requirement, technical difficulty big, High cost, poor safety performance.
The content of the invention
It is an object of the invention to provide a kind of preparation process it is simple, condition is easily-controllable, Fe with low cost2O3Nanotube it is sacrificial Domestic animal template preparation technology, to obtain the Fe that crystal formation is good, photocatalysis performance is high2O3Nanotube.
The purpose of the present invention is realized in the following way：Autocatalyzed oxidation reduction reaction is first carried out on FTO glass FTO/Cu precipitations are obtained, the precipitation is then carried out into anodic oxidation and is obtained FTO/Cu (OH)2Nano wire, finally by FTO/Cu (OH)2 Nano wire via high annealing under blanket of nitrogen, etching, again the process of high annealing obtain Fe2O3Nanotube.Specifically include following Step：
（1）The FTO glass that will be cleaned up is placed in the concentration respectively CuSO of 10-15g/L4, 10-15g/L NaCO3、40- In the mixed aqueous solution of the sodium potassium tartrate tetrahydrate of 45g/L and two second bipyridines of 10-20mg/L, it is subsequently adding 15-20mL's HCHO soaks 3-4h, makes Cu in solution2+Autocatalyzed oxidation reduction reaction, generation FTO/Cu precipitations are carried out with HCHO；
（2）By step（1）In the NaOH solution of middle FTO/Cu immersion 0.5mol/L, in reacting 1- under the constant voltage of 20-40V 2h, obtains FTO/Cu (OH)2Nano wire；
（3）By step（2）Middle FTO/ Cu (OH)2Nano wire is warming up to 500-600 DEG C with the speed of 2 DEG C/min under nitrogen atmosphere, And 4-5h is kept, obtain FTO/CuO nano wires；
（4）By step（3）Middle FTO/CuO nano wires immerse the FeCl of 0.05-0.15mol/L3·6H2O and 0.1-0.2mol/L NaCl mixed solution in, react 12-24h under normal temperature, obtain FeOOH；
（5）By step（4）Middle FeOOH is placed in tube furnace, and 550-600 DEG C is warming up to the speed of 2 DEG C/min, keeps 2- 2.5h, you can obtain Fe2O3Nanotube.
Present invention selection FTO electro-conductive glass is base material, by the use of CuO nano wires as template is sacrificed, with FeCl3· 6H2O is that source of iron prepares Fe2O3Nanotube, preparation process is simple, and easily-controlled experimental conditions, whole preparation process is high without price High equipment, with low cost, obtained Fe2O3Nanotube has good crystal formation, and photocatalytic activity is high.
Brief description of the drawings
Fig. 1 is the Fe prepared using method in the embodiment of the present invention 12O3The SEM figures of nanotube.
Fig. 2 is the Fe prepared using method in the embodiment of the present invention 12O3The density of photocurrent figure of nanotube.
Specific embodiment
For a better understanding of the present invention, the invention will be further described with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
Fe2O3The sacrifice template method of nanotube prepares technique, comprises the following steps：
（1）FTO glass is cut into the square of 2.5 cm × 1.5 cm sizes, first with detergent water supersound washing 3 times, every time 20 Min, to remove surface and oil contaminant；Then ultrasonic 3 times with distilled water and deionized water respectively, 20 min, removes FTO surfaces every time Impurity；It is finally ultrasonic 3 times with absolute ethyl alcohol, the organic impurities on FTO surfaces is removed, sealing preserve is standby after nitrogen drying；
（2）The FTO glass that will be cleaned up is placed in the concentration respectively CuSO of 10g/L4, 10g/L NaCO3, 40g/L wine In the mixed aqueous solution of two second bipyridines of stone acid potassium sodium and 10mg/L, the HCHO immersion 3h of 15mL are subsequently adding, make solution Middle Cu2+Autocatalyzed oxidation reduction reaction, generation FTO/Cu precipitations are carried out with HCHO；
（3）By step（2）In the NaOH solution of middle FTO/Cu immersions 0.5mol/L, in 2h is reacted under the constant voltage of 40V, obtain To FTO/Cu (OH)2Nano wire；
（4）By step（3）Middle FTO/ Cu (OH)2Nano wire is warming up to 500 DEG C with the speed of 2 DEG C/min under nitrogen atmosphere, keeps 4h, obtains FTO/CuO nano wires；
（5）By step（4）Middle FTO/CuO nano wires immerse the FeCl of 0.05mol/L3·6H2The NaCl's of O and 0.1mol/L is mixed Close in solution, 24h is reacted under normal temperature, obtain FeOOH；
（6）By step（5）Middle FeOOH is placed in tube furnace, and 550 DEG C are warming up to the speed of 2 DEG C/min, keeps 2h, you can To Fe2O3Nanotube.Scanning electron microscope (SEM) photograph（Fig. 1）Show the Fe2O3Nanotube has good crystal formation, density of photocurrent figure（Fig. 2） It has been shown that, works as Fe2O3Its density of photocurrent is about 0.57mAcm when the standard hydrogen electrode potential of nanotube is 1.23V-2, and reported Road document（Zhuofeng Hu, Zhurui Shen, and Jimmy C. Yu, Covalent Fixation of Surface Oxygen Atoms on Hematite Photoanode for Enhanced Water Oxidation. Chem. Mater.2016, 28, 564-572.）Middle Fe2O3Its density of photocurrent is when the standard hydrogen electrode potential of nanometer rods is 1.23V 0.25mA·cm-2, the result shows the Fe prepared using method in the present embodiment2O3Nanotube has good photoelectric properties, Photocatalytic activity is high.
Embodiment 2
Fe2O3The sacrifice template method of nanotube prepares technique, comprises the following steps：
（1）Using with the step of embodiment 1（1）Middle identical method cleans FTO glass；
（2）The FTO glass that will be cleaned up is placed in the concentration respectively CuSO of 10g/L4, 10g/L NaCO3, 40g/L wine In the mixed aqueous solution of two second bipyridines of stone acid potassium sodium and 15mg/L, the HCHO immersion 3.5h of 15mL are subsequently adding, made molten Cu in liquid2+Autocatalyzed oxidation reduction reaction, generation FTO/Cu precipitations are carried out with HCHO；
（3）By step（2）In the NaOH solution of middle FTO/Cu immersion 0.5mol/L, in reacting 1.5h under the constant voltage of 30V, Obtain FTO/Cu (OH)2Nano wire；
（4）By step（3）Middle FTO/ Cu (OH)2Nano wire is warming up to 550 DEG C with the speed of 2 DEG C/min under nitrogen atmosphere, keeps 4.5h, obtains FTO/CuO nano wires；
（5）By step（4）Middle FTO/CuO nano wires immerse the FeCl of 0.10mol/L3·6H2The NaCl's of O and 0.15mol/L In mixed solution, 18h is reacted under normal temperature, obtain FeOOH；
（6）By step（5）Middle FeOOH is placed in tube furnace, and 550 DEG C are warming up to the speed of 2 DEG C/min, keeps 2h, you can To Fe2O3Nanotube.
Embodiment 3
Fe2O3The sacrifice template method of nanotube prepares technique, comprises the following steps：
（1）Using with the step of embodiment 1（1）Middle identical method cleans FTO glass；
（2）The FTO glass that will be cleaned up is placed in the concentration respectively CuSO of 15g/L4, 15g/L NaCO3, 45g/L wine In the mixed aqueous solution of two second bipyridines of stone acid potassium sodium and 20mg/L, the HCHO immersion 4.0h of 20mL are subsequently adding, made molten Cu in liquid2+Autocatalyzed oxidation reduction reaction, generation FTO/Cu precipitations are carried out with HCHO；
（3）By step（2）In the NaOH solution of middle FTO/Cu immersion 0.5mol/L, in reacting 1.0h under the constant voltage of 20V, Obtain FTO/Cu (OH)2Nano wire；
（4）By step（3）Middle FTO/ Cu (OH)2Nano wire is warming up to 600 DEG C with the speed of 2 DEG C/min under nitrogen atmosphere, keeps 5.0h, obtains FTO/CuO nano wires；
（5）By step（4）Middle FTO/CuO nano wires immerse the FeCl of 0.15mol/L3·6H2The NaCl's of O and 0.20mol/L In mixed solution, 24h is reacted under normal temperature, obtain FeOOH；
（6）By step（5）Middle FeOOH is placed in tube furnace, and 600 DEG C are warming up to the speed of 2 DEG C/min, keeps 2.5h, you can Obtain Fe2O3Nanotube.

Claims (1)

1.Fe2O3The sacrifice template method of nanotube prepares technique, it is characterised in that comprise the following steps：
（1）The FTO glass that will be cleaned up is placed in the concentration respectively CuSO of 10-15g/L4, 10-15g/L NaCO3、40- In the mixed aqueous solution of the sodium potassium tartrate tetrahydrate of 45g/L and two second bipyridines of 10-20mg/L, it is subsequently adding 15-20mL's HCHO soaks 3-4h, makes Cu in solution2+Autocatalyzed oxidation reduction reaction, generation FTO/Cu precipitations are carried out with HCHO；
（2）By step（1）In the NaOH solution of middle FTO/Cu immersion 0.5mol/L, in reacting 1- under the constant voltage of 20-40V 2h, obtains FTO/Cu (OH)2Nano wire；
（3）By step（2）Middle FTO/ Cu (OH)2Nano wire is warming up to 500-600 DEG C with the speed of 2 DEG C/min under nitrogen atmosphere, And 4-5h is kept, obtain FTO/CuO nano wires；
（4）By step（3）Middle FTO/CuO nano wires immerse the FeCl of 0.05-0.15mol/L3·6H2O's and 0.1-0.2mol/L In the mixed solution of NaCl, 12-24h is reacted under normal temperature, obtain FeOOH；
（5）By step（4）Middle FeOOH is placed in tube furnace, and 550-600 DEG C is warming up to the speed of 2 DEG C/min, keeps 2- 2.5h, you can obtain Fe2O3Nanotube.
CN201710042773.XA 2017-01-20 2017-01-20 Fe2O3The sacrifice template method of nanotube prepares technique Expired - Fee Related CN106698523B (en)

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