CN103160900B - One prepares Fe in conductive substrates 2o 3the method of nano-tube array - Google Patents
One prepares Fe in conductive substrates 2o 3the method of nano-tube array Download PDFInfo
- Publication number
- CN103160900B CN103160900B CN201310059785.5A CN201310059785A CN103160900B CN 103160900 B CN103160900 B CN 103160900B CN 201310059785 A CN201310059785 A CN 201310059785A CN 103160900 B CN103160900 B CN 103160900B
- Authority
- CN
- China
- Prior art keywords
- nano
- tube array
- feooh
- electrode
- conductive substrates
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The present invention relates to and prepare Fe in conductive substrates
2o
3the method of nano-tube array.The present invention be loaded with ZnO nano-rod array conductive substrates as working electrode, using platinized platinum as to electrode, using saturated calomel electrode as reference electrode, with containing FeCl
2the aqueous solution as electrolytic solution; By applying constant positive potential (relative to reference electrode) to described working electrode, the Fe2+ in the electrolytic solution near working electrode is made to be oxidized to Fe
3+and forming FeOOH throw out, FeOOH throw out constantly deposits on the surface of ZnO nanorod, and ZnO nanorod dissolves until completely dissolve gradually simultaneously, forms FeOOH nano-tube array, thus obtains growing the conductive substrates having FeOOH nano-tube array; Then in tube furnace, carry out high temperature annealing, make FeOOH nano-tube array be converted into Fe
2o
3nano-tube array, conductive substrates obtains Fe
2o
3nano-tube array.
Description
Technical field
The invention belongs to semiconductor nano material preparation field, particularly relate to and prepare Fe in conductive substrates
2o
3the method of nano-tube array.
Background technology
Fe
2o
3a kind of narrow gap semiconductor (E
g=1.9 ~ 2.0eV), be with a wide range of applications in fields such as photoelectrocatalysis water of decomposition, lithium ion battery, gas sensings (Nano Letter, 2011,11,3503; Advanced Materials, 2005,17,2993.).In photochemical catalyzing field, Fe
2o
3primary limitation be its very poor electroconductibility, short photo-generated carrier life-span, and very short current carrier effectively collects length (a few nanometer scale), and this causes Fe
2o
3most of photo-generated carrier of interior generation all can lose because of body phase compound, thus can not be transferred to Fe
2o
3/ electrolyte interface participates in photocatalytic water reaction (Chemsuschem, 2011,4,432.).Research proves, nano-tube array has good antireflective effect, can improve total photoabsorption; Secondly, in nano-tube array, the collection length of photo-generated carrier is only the thickness of nanotube tube wall, substantially reduces the distance that photo-generated carrier is transferred to electrolytic solution in body, decreases its body phase compound; Again, nano-tube array expands the useful area of electrode, is also conducive to increasing photoelectric current.In addition, in field of lithium ion battery, research proves Fe
2o
3nanotube not only expands the useful area of electrode, and the volumetric expansion that its special hollow structure also can be repeatedly electrode materials in charge and discharge process provides clearance spaces, the material efflorescence that can effectively prevent repeatedly discharge and recharge from causing, structure collapses, thus improves Fe
2o
3stability in repeatedly charge and discharge cycles.
Based on Fe
2o
3the excellent properties of nano-tube array and wide application prospect, the invention provides one electrochemical deposition technique and prepare Fe in conductive substrates
2o
3the method of nano-tube array.Relative to other preparation method, electrochemical deposition has better controllability, without the need to extreme experiment condition; In addition, electrochemical deposition strongthener granular boundary place, material can contact with the electricity at substrate interface place, thus is conducive to Fe
2o
3material is in the application in the field such as photoelectrocatalysis, lithium ion battery.
Summary of the invention
The object of this invention is to provide one and prepare Fe in conductive substrates
2o
3the method of nano-tube array.
The present invention be loaded with ZnO nano-rod array conductive substrates as working electrode, using platinized platinum as to electrode, using saturated calomel electrode as reference electrode, with containing FeCl
2the aqueous solution as electrolytic solution; By applying constant positive potential (relative to reference electrode) to described working electrode, make the Fe in the electrolytic solution near working electrode
2+be oxidized to Fe
3+and form FeOOH throw out, FeOOH throw out constantly deposits on the surface of ZnO nanorod, ZnO nanorod simultaneously dissolves until completely dissolve due to the acidity of electrolytic solution and the impact of positive potential that applies gradually, form FeOOH nano-tube array, thus obtain growing the conductive substrates having FeOOH nano-tube array; Then in tube furnace, have the conductive substrates of FeOOH nano-tube array to carry out high temperature annealing to described growth, make FeOOH nano-tube array be converted into Fe
2o
3nano-tube array, conductive substrates obtains Fe
2o
3nano-tube array.
Of the present inventionly in conductive substrates, prepare Fe
2o
3the method of nano-tube array comprises the following steps:
(1) electrochemical deposition prepares FeOOH nano-tube array: to be loaded with the conductive substrates of ZnO nano-rod array as working electrode, using platinized platinum as to electrode, using saturated calomel electrode as reference electrode, with containing FeCl
2the aqueous solution as electrolytic solution; Constant positive potential (relative to reference electrode) is applied to described working electrode, makes the Fe near working electrode in electrolytic solution
2+be oxidized to Fe
3+and form FeOOH throw out, FeOOH throw out constantly deposits on the surface of ZnO nanorod, ZnO nanorod simultaneously dissolves until completely dissolve due to the acidity of electrolytic solution and the impact of positive potential that applies gradually, form FeOOH nano-tube array, obtain growing the conductive substrates having FeOOH nano-tube array;
(2) Fe
2o
3prepared by nano-tube array: have the conductive substrates of FeOOH nano-tube array to put into tube furnace the growth that step (1) obtains and carry out high temperature annealing, make FeOOH nano-tube array be converted into Fe
2o
3nano-tube array, conductive substrates obtains Fe
2o
3nano-tube array.
Described in step (1) containing FeCl
2the aqueous solution in FeCl
2concentration be 5 ~ 15mM.Described contains FeCl
2the temperature of the aqueous solution be 50 ~ 80 DEG C.
The time of the constant positive potential of applying (relative to reference electrode) described in step (1) is preferably 2 ~ 20 minutes.The size of described positive potential (relative to reference electrode) is that 0.95 ~ 1.15V(is relative to reference electrode).
The temperature of the high temperature annealing described in step (2) is 500 DEG C ~ 800 DEG C.
Described conductive substrates is the substrate of FTO conductive glass.
Of the present inventionly in conductive substrates, prepare Fe
2o
3the method superiority of nano-tube array is: preparation process is without the need to the high-vacuum apparatus such as such as magnetron sputtering, ald etc. of complexity, and method is simple, feasibility is high; Secondly, raw materials is environmental friendliness, cheap chemical substance; In addition, electrochemical deposition strongthener granular boundary place, material can contact with the electricity at substrate interface place, thus is conducive to Fe
2o
3material is in the application in the field such as photoelectrocatalysis, lithium ion battery.
Accompanying drawing explanation
Fig. 1. the scanning electron microscope diagram sheet of ZnO nano-rod array prepared by the embodiment of the present invention 1, (a) vertical view, (b) side-view.
Fig. 2. Fe prepared by the embodiment of the present invention 1
2o
3the scanning electron microscope diagram sheet of nano-tube array, (a) vertical view, (b) side-view.
Fig. 3. Fe prepared by the embodiment of the present invention 1
2o
3the transmission electron micrograph of nano-tube array.
Fig. 4. Fe prepared by the embodiment of the present invention 1
2o
3the X-ray diffraction spectrum of nano-tube array.
Fig. 5. Fe prepared by the embodiment of the present invention 2
2o
3the scanning electron microscope diagram sheet of nano-tube array, (a) vertical view, (b) side-view.
Fig. 6. Fe prepared by the embodiment of the present invention 2
2o
3the transmission electron micrograph of nano-tube array.
Fig. 7. Fe prepared by the embodiment of the present invention 3
2o
3the scanning electron microscope diagram sheet of nano-tube array.
Fig. 8. Fe prepared by the embodiment of the present invention 3
2o
3the transmission electron micrograph of nano-tube array.
Embodiment
Embodiment 1.
The substrate of FTO conductive glass is carried out ultrasonic cleaning successively in acetone, ethanol, water.Using the FTO conductive glass substrate of cleaning as working electrode, using platinized platinum as to electrode, using saturated calomel electrode as reference electrode, with containing 0.2mM Zn (Ac)
2with 0.1M KCL, temperature is 85 DEG C, continues to pass into the aqueous solution of oxygen bubble as electrolytic solution; By applying 2 hours to described working electrode, the negative potential (relative to reference electrode) of-1V, in the substrate of FTO conductive glass, electrochemical deposition obtains ZnO nano-rod array, and scanning electron microscope diagram sheet as shown in Figure 1.
To be loaded with the FTO conductive glass substrate of ZnO nano-rod array as working electrode, using platinized platinum as to electrode, using saturated calomel electrode as reference electrode, with containing 5mM FeCl
2, temperature is that the aqueous solution of 50 DEG C is as electrolytic solution; By applying 0.95V to described working electrode, the positive potential (relative to reference electrode) of 2 minutes, makes the Fe in the electrolytic solution near working electrode
2+be oxidized to Fe
3+and form FeOOH throw out, FeOOH throw out constantly deposits on the surface of ZnO nanorod, simultaneously ZnO nanorod dissolves until completely dissolve due to the acidity of electrolytic solution and the impact of positive potential that applies gradually, form FeOOH nano-tube array, thus obtain growing the FTO conductive glass substrate having FeOOH nano-tube array; There is the FTO conductive glass substrate of FeOOH nano-tube array to put into tube furnace growth, at 500 DEG C, carry out high temperature annealing 2 hours, make FeOOH nano-tube array be converted into Fe
2o
3nano-tube array, the substrate of FTO conductive glass obtains Fe
2o
3nano-tube array.
Gained Fe
2o
3as shown in Figure 2, as shown in Figure 3, X-ray diffraction spectrum as shown in Figure 4 for transmission electron micrograph for the scanning electron microscope diagram sheet of nano-tube array.
Embodiment 2.
The substrate of FTO conductive glass is carried out ultrasonic cleaning successively in acetone, ethanol, water.Using the FTO conductive glass substrate of cleaning as working electrode, using platinized platinum as to electrode, using saturated calomel electrode as reference electrode, with containing 0.2mM Zn (Ac)
2with 0.1M KCL, temperature is 85 DEG C, continues to pass into the aqueous solution of oxygen bubble as electrolytic solution; By applying 2 hours to described working electrode, the negative potential (relative to reference electrode) of-1V, in the substrate of FTO conductive glass, electrochemical deposition obtains ZnO nano-rod array.
To be loaded with the FTO conductive glass substrate of ZnO nano-rod array as working electrode, using platinized platinum as to electrode, using saturated calomel electrode as reference electrode, with containing 10mM FeCl
2, temperature is that the aqueous solution of 70 DEG C is as electrolytic solution; By applying 1V to described working electrode, the positive potential (relative to reference electrode) of 10 minutes, makes the Fe in the electrolytic solution near working electrode
2+be oxidized to Fe
3+and form FeOOH throw out, FeOOH throw out constantly deposits on the surface of ZnO nanorod, simultaneously ZnO nanorod dissolves until completely dissolve due to the acidity of electrolytic solution and the impact of positive potential that applies gradually, form FeOOH nano-tube array, thus obtain growing the FTO conductive glass substrate having FeOOH nano-tube array; There is the FTO conductive glass substrate of FeOOH nano-tube array to put into tube furnace growth, at 600 DEG C, carry out high temperature annealing 2 hours, make FeOOH nano-tube array be converted into Fe
2o
3nano-tube array, the substrate of FTO conductive glass obtains Fe
2o
3nano-tube array.
Gained Fe
2o
3as shown in Figure 5, transmission electron micrograph as shown in Figure 6 for the scanning electron microscope diagram sheet of nano-tube array.
Embodiment 3.
The substrate of FTO conductive glass is carried out ultrasonic cleaning successively in acetone, ethanol, water.Using the FTO conductive glass substrate of cleaning as working electrode, using platinized platinum as to electrode, using saturated calomel electrode as reference electrode, with containing 0.2mM Zn (Ac)
2with 0.1M KCL, temperature is 85 DEG C, continues to pass into the aqueous solution of oxygen bubble as electrolytic solution; By applying 2 hours to described working electrode, the negative potential of-1V, in the substrate of FTO conductive glass, electrochemical deposition obtains ZnO nano-rod array.
To be loaded with the FTO conductive glass substrate of ZnO nano-rod array as working electrode, using platinized platinum as to electrode, using saturated calomel electrode as reference electrode, with containing 15mM FeCl
2, temperature is that the aqueous solution of 80 DEG C is as electrolytic solution; By applying 1.15V to described working electrode, the positive potential (relative to reference electrode) of 20 minutes, makes the Fe in the electrolytic solution near working electrode
2+be oxidized to Fe
3+and form FeOOH throw out, FeOOH throw out constantly deposits on the surface of ZnO nanorod, simultaneously ZnO nanorod dissolves until completely dissolve due to the acidity of electrolytic solution and the impact of positive potential that applies gradually, form FeOOH nano-tube array, thus obtain growing the FTO conductive glass substrate having FeOOH nano-tube array; There is the FTO conductive glass substrate of FeOOH nano-tube array to put into tube furnace growth, at 800 DEG C, carry out high temperature annealing 2 hours, make FeOOH nano-tube array be converted into Fe
2o
3nano-tube array, the substrate of FTO conductive glass obtains Fe
2o
3nano-tube array.
Gained Fe
2o
3as shown in Figure 7, transmission electron micrograph as shown in Figure 8 for the scanning electron microscope diagram sheet of nano-tube array.
Claims (5)
1. in conductive substrates, prepare Fe for one kind
2o
3the method of nano-tube array, is characterized in that, described preparation method comprises the following steps:
(1) to be loaded with the conductive substrates of ZnO nano-rod array as working electrode, using platinized platinum as to electrode, using saturated calomel electrode as reference electrode, being 5 ~ 15mM FeCl containing concentration
2the aqueous solution as electrolytic solution; Be the constant positive potential of 0.95 ~ 1.15V relative to reference electrode size to working electrode applying, make the Fe in the electrolytic solution near described working electrode
2+be oxidized to Fe
3+and forming FeOOH throw out, FeOOH throw out constantly deposits on the surface of described ZnO nanorod, and ZnO nanorod dissolves until completely dissolve gradually simultaneously, forms FeOOH nano-tube array, obtains growing the conductive substrates having FeOOH nano-tube array;
(2) there is the conductive substrates of FeOOH nano-tube array to put into tube furnace the growth that step (1) obtains and carry out high temperature annealing, make FeOOH nano-tube array be converted into Fe
2o
3nano-tube array, conductive substrates obtains Fe
2o
3nano-tube array.
2. method according to claim 1, is characterized in that: described contains FeCl
2the temperature of the aqueous solution be 50 ~ 80 DEG C.
3. method according to claim 1, is characterized in that: described applies relative to the time of the constant positive potential of reference electrode to be 2 ~ 20 minutes to working electrode.
4. method according to claim 1, is characterized in that: the temperature of described high temperature annealing is 500 DEG C ~ 800 DEG C.
5. method according to claim 1, is characterized in that: described conductive substrates is the substrate of FTO conductive glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310059785.5A CN103160900B (en) | 2013-02-26 | 2013-02-26 | One prepares Fe in conductive substrates 2o 3the method of nano-tube array |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310059785.5A CN103160900B (en) | 2013-02-26 | 2013-02-26 | One prepares Fe in conductive substrates 2o 3the method of nano-tube array |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103160900A CN103160900A (en) | 2013-06-19 |
| CN103160900B true CN103160900B (en) | 2015-11-04 |
Family
ID=48584420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310059785.5A Active CN103160900B (en) | 2013-02-26 | 2013-02-26 | One prepares Fe in conductive substrates 2o 3the method of nano-tube array |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103160900B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105780087B (en) * | 2014-12-16 | 2018-03-20 | 中国科学院大连化学物理研究所 | The preparation method of Electric oxidative synthesis 1-dimention nano oxide structure |
| CN105990560B (en) * | 2015-02-09 | 2018-04-27 | 北京大学 | Ferric oxide multi-porous nano-bar array electrode material and preparation method thereof |
| CN105251490B (en) * | 2015-11-06 | 2017-10-13 | 国家电网公司 | α Fe are prepared based on hydro-thermal method2O3The method of nano-tube array |
| CN105931852B (en) * | 2016-04-21 | 2018-02-06 | 三峡大学 | A kind of surface is in di-iron trioxide nano-tube array material of lint shape and preparation method thereof |
| CN106006756B (en) * | 2016-05-19 | 2017-07-04 | 青岛大学 | A kind of Fe2O3The preparation method of nano thin-film crimp tube |
| CN106350846B (en) * | 2016-09-19 | 2018-06-22 | 长春理工大学 | Prepared by a kind of electrochemical deposition patterns orderly α-Fe2O3The method of nano particles array |
| CN107326385B (en) * | 2017-06-16 | 2019-01-22 | 中国科学院化学研究所 | A kind of preparation method of boron doping di-iron trioxide optoelectronic pole |
| CN110257855A (en) * | 2019-06-03 | 2019-09-20 | 北京化工大学 | A kind of method that integration carries out Regenrable catalyzed electrode preparation and long-acting electrocatalytic reaction |
| CN110438526A (en) * | 2019-07-17 | 2019-11-12 | 福建师范大学 | A kind of preparation method of nanogold codope iron oxide composite catalyzing electrode, catalysis electrode and electrolysis wetting system |
| CN110371924B (en) * | 2019-07-25 | 2022-06-14 | 许昌学院 | Fe2O3 porous nanowire electrode material, preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101148271A (en) * | 2007-05-31 | 2008-03-26 | 中国科学院电工研究所 | Preparation method for gamma-Fe2O3 nano-tube |
-
2013
- 2013-02-26 CN CN201310059785.5A patent/CN103160900B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101148271A (en) * | 2007-05-31 | 2008-03-26 | 中国科学院电工研究所 | Preparation method for gamma-Fe2O3 nano-tube |
Non-Patent Citations (3)
| Title |
|---|
| Controlled synthesis of oriented single-crystal ZnO nanotube arrays on transparent conductive substrates;Guana-Wei She et al.;《APPLIED PHYSICS FETTERS》;20080208;第92卷;第053111-1页右栏第1-2段，第053111-2页右栏第1段，图2 * |
| Photoactivity of Transparent Nanocrystalline Fe2O3 Electrodes Prepared via Anodic Electrodeposition;Ryan L.Sprayet al.;《Chem.Mater》;20090714;第21卷;第3702页右栏第2-3段，第3703页左栏第2段和右栏第3段 * |
| α-Fe2O3 nanotubes with superior lithium storage capability;Zhiyu Wang et al.;《Chem.Commum》;20110616;第47卷;第8061段右栏第2段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103160900A (en) | 2013-06-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103160900B (en) | One prepares Fe in conductive substrates 2o 3the method of nano-tube array | |
| Govindasamy et al. | Fabrication of hierarchical NiCo2S4@ CoS2 nanostructures on highly conductive flexible carbon cloth substrate as a hybrid electrode material for supercapacitors with enhanced electrochemical performance | |
| Zheng et al. | Three-birds-with-one-stone electrolysis for energy-efficiency production of gluconate and hydrogen | |
| Yang et al. | Highly efficient electrochemical degradation of perfluorooctanoic acid (PFOA) by F-doped Ti/SnO2 electrode | |
| Zhu et al. | Photocathodic protection properties of three-dimensional titanate nanowire network films prepared by a combined sol–gel and hydrothermal method | |
| Yan et al. | MnO2 film with three-dimensional structure prepared by hydrothermal process for supercapacitor | |
| Feng et al. | Nickel-coated silicon photocathode for water splitting in alkaline electrolytes | |
| Zhang et al. | Remarkable supercapacitive performance of TiO2 nanotube arrays by introduction of oxygen vacancies | |
| Yang et al. | Enhanced performance of photoelectrochemical water splitting with ITO@ α-Fe2O3 core–shell nanowire array as photoanode | |
| Huang et al. | Electrochemical properties of MnO2-deposited TiO2 nanotube arrays 3D composite electrode for supercapacitors | |
| Gao et al. | Synergistic effects in three-dimensional SnO2/TiO2/CdS multi-heterojunction structure for highly efficient photoelectrochemical hydrogen production | |
| Sagu et al. | Anodized steel electrodes for supercapacitors | |
| CN105845462B (en) | Preparation method based on three-dimensional grapheme/mangano-manganic oxide combination electrode material | |
| Krishnamoorthy et al. | Hydrothermal synthesis, characterization and electrochemical properties of cobalt sulfide nanoparticles | |
| CN108546970B (en) | Bi2Se3/TiO2Nano composite film and preparation and application thereof | |
| Kwon et al. | Tungsten disulfide thin film/p-type Si heterojunction photocathode for efficient photochemical hydrogen production | |
| Xing et al. | Influence of substrate morphology on the growth and properties of TiO2 nanotubes in HBF4-based electrolyte | |
| Zhao et al. | Boosting the performance of flexible in-plane micro-supercapacitors by engineering MoS2 nanoparticles embedded in laser-induced graphene | |
| CN105986292B (en) | Preparation method of cobalt-nickel double-layer hydroxide modified titanium dioxide nanotube array and application of photoelectrochemical hydrolysis hydrogen production | |
| CN105185598B (en) | A kind of Mn for ultracapacitor3O4/TiO2Nanometer tube composite materials and preparation method thereof | |
| Wu et al. | A high performance asymmetric supercapacitor based on carbon fiber coated with MgCo2O4 nanobrush | |
| Li et al. | Applications of plasma-assisted systems for advanced electrode material synthesis and modification | |
| Liu et al. | Ultrafast fabrication of nanostructure WO3 photoanodes by hybrid microwave annealing with enhanced photoelectrochemical and photoelectrocatalytic activities | |
| CN105845463B (en) | Preparation method based on three-dimensional grapheme/nickel hydroxide composite electrode material | |
| Guo et al. | Solvothermal fabrication of three-dimensionally sphere-stacking Sb–SnO2 electrode based on TiO2 nanotube arrays |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |