CN108574129A - A kind of high temperature resistant calcining iron oxide nanotube electrode and its preparation method and application - Google Patents
A kind of high temperature resistant calcining iron oxide nanotube electrode and its preparation method and application Download PDFInfo
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- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a kind of high temperature resistant calcining iron oxide nanotube electrode and its preparation method and application, Fe of the high temperature resistant calcining iron oxide nanotube electrode by vertical-growth on electro-conductive glass2O3Nano-tube array and in Fe2O3In-stiu coating Fe around nanometer pipe outer wall2O3ZrO2Nanocrystal forms, and ferric trichloride and sodium nitrate aqueous solution are tuned into after acidity and carry out reflection generation FeOOH nanometer stick arrays in electro-conductive glass substrate, and then the method through atomic layer deposition coats ZrO around FeOOH nanometer rods2Nanocrystal, is finally made high temperature resistant calcining iron oxide nanotube electrode by high-temperature roasting, which has good photoelectric properties.The present invention is simple and practicable, each step is accurate adjustable, and by adjusting the time of hydrothermal synthesis, the length of the controllable FeOOH nanometer rods synthesized is to can control the thickness of entire electrode, by the way that temperature, time and the periodicity of atomic layer deposition is arranged, ZrO is adjusted2Thickness, the present invention is relative to traditional Fe2O3There are better photoelectric properties.
Description
Technical field
The invention belongs to the semi-conducting electrode field of photoelectrochemistrpool pool, specially a kind of high temperature resistant roasting oxidation iron nanotube
Electrode and its preparation method and application.
Background technology
1-dimention nano tube material, since its special optics and electromagnetic property are studied extensively1.Iron oxide, especially
It is hematite-type α-Fe2O3, it is widely applied in the energy and environmental area2.Wherein, Fe2O3Nanotube is in lithium-ion electric
Pond3, chemical sensor4With photolysis water hydrogen electrode5On receive people concern.
Research shows that high-temperature roasting has vital effect to promoting oxidation ferrum property.High-temperature roasting can be carried significantly
High Fe2O3The crystallinity of material, to improve the transmission of its carrier, the susceptibility of sensing and the absorption coefficient to sunlight.
In photocatalytic water electrode field, high-temperature roasting (>=750 DEG C) can effectively improve Fe2O3The take-off potential of electrode6And photogenerated current7。
However, high-temperature roasting can cause Fe2O3Structural damage can especially cause the reunion of nano particle8。
Therefore, the Fe of high temperature resistant roasting is prepared2O3Nanotube is scientific and technical problem urgently to be resolved hurrily.Currently, not yet first
Example successfully prepares the Fe of high temperature resistant roasting2O3Nanotube.
1 a)G.R.Patzke,F.Krumeich,R.Nesper,Angew.Chem.Int.Ed.2002,41,2446-
2461；b)Y.Xia,P.Yang,Y.Sun,Y.Wu,B.Mayers,B.Gates,Y.Yin,F.Kim,H.Yan,
Adv.Mater.2003,15,353-389.
2 C.Wu,P.Yin,X.Zhu,C.OuYang,Y.Xie,J.Phys.Chem.B 2006,110,17806-17812.
3 N.Kang,J.H.Park,J.Choi,J.Jin,J.Chun,I.G.Jung,J.Jeong,J.-G.Park,
S.M.Lee,H.J.Kim,S.U.Son,Angew.Chem.Int.Ed.2012,51,6626-6630.
4 Z.Sun,H.Yuan,Z.Liu,B.Han,X.Zhang,Adv.Mater.2005,17,2993-2997.
5 G.K.Mor,H.E.Prakasam,O.K.Varghese,K.Shankar,C.A.Grimes,Nano
Lett.2007,7,2356-2364.
6 J.-W.Jang,C.Du,Y.Ye,Y.Lin,X.Yao,J.Thorne,E.Liu,G.McMahon,J.Zhu,
A.Javey,J.Guo,D.Wang,Nat.Commun.2015,6,7447.
7 J.Y.Kim,G.Magesh,D.H.Youn,J.-W.Jang,J.Kubota,K.Domen,J.S.Lee,
Sci.Rep.2013,3,2681.
8 K.Sivula,R.Zboril,F.Le Formal,R.Robert,A.Weidenkaff,J.Tucek,
J.Frydrych,M.J.Am.Chem.Soc.2010,132,7436-7444.
Invention content
It is an object of the invention to overcome deficiency in the prior art, a kind of high temperature resistant roasting oxidation iron nanotube is provided
Electrode and its preparation method and application, the present invention is simple and easy to do, and controllability is strong, environmentally friendly, and energy consumption is smaller, it can be achieved that big
Large-scale production.
In order to solve the above-mentioned technical problem, the present invention is achieved by technical solution below：
A kind of high temperature resistant calcining iron oxide nanotube electrode, by Fe of the vertical-growth on electro-conductive glass2O3Nano-tube array
With in Fe2O3In-stiu coating Fe around nanometer pipe outer wall2O3ZrO2Nanocrystal forms；The high temperature resistant calcining iron oxide is received
Mitron thickness of electrode and Fe2O3Nano-tube array is highly consistent, is 330~355nm；Fe2O3The outer diameter of nanotube be 50~
55nm, ZrO215~20nm of nano film thickness.
A kind of preparation method of high temperature resistant calcining iron oxide nanotube electrode, steps are as follows：
Step 1 mixes the sodium nitrate aqueous solution of the ferric trichloride of a concentration of 0.1~0.2mol/L and 1~2mol/L,
The pH of mixed solution is adjusted to 1.1~1.5, as the precursor solution for preparing FeOOH nanometer rods；
Electro-conductive glass substrate is put into the precursor solution described in step 1 by step 2, reacts 6 at 95~100 DEG C
~12h, gained are the FeOOH nanometer stick arrays of the homoepitaxial in electro-conductive glass substrate；
FeOOH nanometer stick arrays described in step 2 are placed in the cavity of atomic layer deposition system and carry out by step 3
Deposition, presoma used are four (ethyl-methyl amido) zirconiums (IV) and water, and number of deposition cycles was 10~50 periods, each to deposit
The depositing temperature in period is 150~300 DEG C, and the time that is passed through of four (ethyl-methyl amido) zirconiums (IV) is 0.1~5s, corresponding carrier gas
Scavenging period is 5~20s, and the time that is passed through of presoma water is 0.01~1s, and corresponding carrier gas scavenging period is 10~30s；This step
It is rapid to realize in one layer of ZrO of FeOOH nanometer stick arrays coated with uniform2Film obtains the FeOOH- in electro-conductive glass substrate
ZrO2Nanometer stick array；
Step 4, by the FeOOH-ZrO described in step 32Sample high-temperature roasting in air, the temperature of high-temperature roasting
It it is 760~840 DEG C, roasting time is to finally obtain ZrO in 6~14 minutes2-Fe2O3The i.e. described high temperature resistant roasting oxidation of nanotube
Iron nanotube electrode.
Moreover, in step 1, the pH of mixed solution is adjusted to 1.2~1.3.
Moreover, the reaction time in step 2 is preferably 11~12h.
Moreover, the sedimentation cycle number in step 3 is preferably 10~40.
Moreover, the condition of the high-temperature roasting described in step 4 is preferably 790~810 DEG C of calcination temperature, roasting time 9~
11 minutes.
A kind of application of high temperature resistant calcining iron oxide nanotube electrode in optical electro-chemistry, the high temperature resistant roasting oxidation
Iron nanotube electrode is as working electrode, and platinum plate electrode is used as to electrode, and silver/silver chloride electrode is reference electrode, by three's group
Photoelectrochemistrpool pool is dressed up, electrolyte is the KOH aqueous solutions of 1~2mol/L, is obtained using the xenon lamp collocation AM 1.5G optical filters of 300W
Simulated solar irradiation is obtained, density of photocurrent is up to 0.7~1.5mA/cm when electrode activity is higher2, at photoelectrochemistrpool pool working electrode
It is 100mW/cm after the irradiated measurement examination of luminous intensity2。
The present invention synthesizes high temperature resistant calcining iron oxide nanotube electrode for the first time, and 1-dimention nano pipe array effectively combines increasing
The problem of big solid liquid interface and carrier separation.Compared with prior art, the present invention is simple and practicable, and each step accurately may be used
It adjusts.By adjusting the time of hydrothermal synthesis, the length of the FeOOH nanometer rods synthesized can be controlled so as to control entire electricity
The thickness of pole can adjust ZrO by the way that temperature, time and the periodicity of atomic layer deposition is arranged2Thickness, roasted by high temperature
It burns, regular high temperature resistant calcining iron oxide nanotube electrode can be obtained.
Description of the drawings
Fig. 1 is the scanning electron microscope sectional view of high temperature resistant calcining iron oxide nanotube electrode in embodiment 1, and scale is
500nm；
Fig. 2 is the scanning electron microscope vertical view of high temperature resistant calcining iron oxide nanotube electrode in embodiment 1, and scale is
500nm；
Fig. 3 is the transmission electron microscope figure of high temperature resistant calcining iron oxide nanotube electrode in embodiment 1, and scale is
10nm；
Fig. 4 (a) is the transmission electron microscope bright field image of high temperature resistant calcining iron oxide nanotube electrode in embodiment 1；(b) it is (a)
Corresponding electron diffraction diagram；(c-f) be (a) corresponding EDS elements Surface scan spectrum, (c), (d), (e) be Fe, O, Zr member respectively
Element, (f) be three kinds of elements stacking chart；(g) it is EDS elemental line scan figures, the region swept is that white arrow is shown the way in (a)
Diameter；
Fig. 5 is the high power transmission electron microscope picture on the outside of high temperature resistant calcining iron oxide nanotube electrode in embodiment 1；
Fig. 6 is high temperature resistant calcining iron oxide nanotube electrode and Fe prepared by embodiment 1 under simulated solar irradiation irradiation2O3It receives
The photoelectron treatment device curve comparison figure of rice rod film electrode.
Specific implementation mode
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
The medicine source used in embodiment is as follows：
Concentrated hydrochloric acid (36.5-38wt%), Iron(III) chloride hexahydrate (FeCl3·6H2O, >=99%), Tianjin recovery fining
Work research institute；
Sodium nitrate (NaNO3, >=99%), Beijing lark prestige Science and Technology Ltd.；
Four (ethyl-methyl amido) zirconiums (TEMAZr, >=99.9999%), nano-electron Science and Technology Ltd. is answered in Suzhou.
The instrument model used in embodiment is as follows：
Scanning electron microscope：FE-SEM, Hitachi S-4800,5kV
Transmission electron microscope：TEM, JEOL JEM-2100F, 200kV
Electrochemical workstation：IVIUM CompactStat
The atomic layer deposition apparatus used in embodiment refer to Chinese invention patent application " a kind of atomic layer deposition apparatus and
Using " (application No. is 2014107494591, applying date 2014.12.09, publication date 2015.04.22).
Embodiment 1
Step 1, high temperature resistant calcining iron oxide nanotube electrode is prepared：
(1) successively ultrasound 10 minutes in deionized water, acetone and ethanol solution successively by FTO electro-conductive glass, through go from
Sub- water is cleaned, and drying is spare；
(2) ferric trichloride and sodium nitrate precursor solution are prepared：2.16g ferric trichlorides and 6.8g sodium nitrate are weighed, is dissolved in
80mL water obtains the mixed solution of 0.1mol/L iron chloride and 1mol/L sodium nitrate；
(3) FTO substrates are put into above-mentioned precursor solution, 12h is reacted at 95 DEG C, elution, drying are obtained in FTO
The uniform FeOOH nanometer stick arrays grown in substrate；
(4) above-mentioned FeOOH samples are placed in the cavity of atomic layer deposition system, presoma used is four (ethyl first
Base amido) zirconium (IV) and water.Opening program is deposited, and the periodicity of deposition was 30 periods, was realized in FeOOH nanometer stick arrays
One layer of ZrO of coated with uniform2Film obtains the FeOOH-ZrO in FTO substrates2Nanometer stick array；
(5) by above-mentioned FeOOH-ZrO2Sample high-temperature roasting in air, using tube furnace, condition is：It 800 DEG C, keeps
10 minutes, Temperature fall obtained high temperature resistant calcining iron oxide nanotube electrode and (is denoted as ZrO2-Fe2O3NT)。
Step 2, Fe is prepared2O3Nanometer stick array：
(1) first synthesize FeOOH nanometer stick arrays, method is the same as (1) in step 1~(3) step；
(2) by above-mentioned FeOOH samples high-temperature roasting in air, using tube furnace, condition is：800 DEG C, kept for 10 points
Clock, Temperature fall obtain Fe2O3Nanometer stick array (is denoted as Fe2O3NR)。
Step 3, by ZrO2-Fe2O3NT and Fe2O3NR is used for photoelectrochemistrpool pool photolysis water hydrogen：
(1) respectively by ZrO2-Fe2O3NT and Fe2O3NR is used as working electrode, platinum plate electrode to electrode, silver/silver chlorate
Electrode is that reference electrode is assembled into photoelectrochemistrpool pool, carries out photoelectric property and photolysis water hydrogen performance test.Electrolyte is 1mol/
The KOH aqueous solutions of L, working electrode illuminating area are 1cm2；
(2) the xenon lamp collocation AM 1.5G optical filters of 300W are used to obtain simulated solar irradiation, at photoelectrochemistrpool pool working electrode
It is 100mW/cm after the irradiated measurement examination of luminous intensity2。
Such as attached drawing 1~2, ZrO is can be seen that from scanning electron microscope sectional view2-Fe2O3NT is regularly grown in
In the FTO substrates of 400nm, thickness, that is, ZrO of ferric oxide nano pipe electrode entirety2-Fe2O3The height of NT is 340~350nm,
Nanometer pipe outer wall is more coarse.
Such as attached drawing 3, from transmission electron microscope figure as can be seen that ZrO2-Fe2O3A diameter of 100 ± the 5nm of NT, wall thickness 20
± 5nm, pipe inside is smoother, and outside is due to there is ZrO2The presence of particle is more coarse.
Such as attached drawing 4, by figure (a-b) it is found that regular dot matrix is Fe2O3Diffractional lattice, point at random is polycrystalline ZrO2's
Point diffraction；The prepared ZrO known to figure (c-g)2-Fe2O3NT contains Fe, O, Zr element and Zr constituent contents are less, Zr elements
In the outside of entire nanotube.
Such as attached drawing 5, there are many ZrO in outside as seen from the figure2Crystal grain, it is relatively rough to cause nanometer pipe outer wall.
Such as attached drawing 6, it is in photoelectron treatment device curve comparison figure the experimental results showed that, in 1.23V (with reversible hydrogen electrode pair
Than) under bias, Fe2O3The density of photocurrent of NR is 0.63mA/cm2；And ZrO2-Fe2O3The density of photocurrent of NT is 1.5mA/
cm2.Thus it proves, through ZrO2-Fe2O3NT is compared to Fe2O3NR has apparent advantage.
Embodiment 2
Step 1, high temperature resistant calcining iron oxide nanotube electrode is prepared：
(1) successively ultrasound 10 minutes in deionized water, acetone and ethanol solution successively by FTO electro-conductive glass, through go from
Sub- water is cleaned, and drying is spare；
(2) ferric trichloride and sodium nitrate precursor solution are prepared：2.16g ferric trichlorides and 6.8g sodium nitrate are weighed, is dissolved in
80mL water obtains the mixed solution of 0.1mol/L iron chloride and 1mol/L sodium nitrate；
(3) FTO substrates are put into above-mentioned precursor solution, 12h is reacted at 95 DEG C, elution, drying are obtained in FTO
The uniform FeOOH nanometer stick arrays grown in substrate；
(4) above-mentioned FeOOH samples are placed in the cavity of atomic layer deposition system, presoma used is four (ethyl first
Base amido) zirconium (IV) and water.Opening program is deposited, and the periodicity of deposition was 10 periods, was realized in FeOOH nanometer stick arrays
One layer of ZrO of coated with uniform2Film obtains the FeOOH-ZrO in FTO substrates2Nanometer stick array；
(5) by above-mentioned FeOOH-ZrO2Sample high-temperature roasting in air, using tube furnace, condition is：It 800 DEG C, keeps
10 minutes, Temperature fall obtained high temperature resistant calcining iron oxide nanotube electrode and (is denoted as ZrO2-Fe2O3NT)。
Step 2, Fe is prepared2O3Nanometer stick array：
(1) first synthesize FeOOH nanometer stick arrays, method is the same as (1) in step 1~(3) step；
(2) by above-mentioned FeOOH samples high-temperature roasting in air, using tube furnace, condition is：800 DEG C, kept for 10 points
Clock, Temperature fall obtain Fe2O3Nanometer stick array (is denoted as Fe2O3NR)。
Step 3, by ZrO2-Fe2O3NT and Fe2O3NR is used for photoelectrochemistrpool pool photolysis water hydrogen：
(1) respectively by ZrO2-Fe2O3NT and Fe2O3NR is used as working electrode, platinum plate electrode to electrode, silver/silver chlorate
Electrode is that reference electrode is assembled into photoelectrochemistrpool pool, carries out photoelectric property and photolysis water hydrogen performance test.Electrolyte is 1mol/
The KOH aqueous solutions of L, working electrode illuminating area are 1cm2；
(2) the xenon lamp collocation AM 1.5G optical filters of 300W are used to obtain simulated solar irradiation, at photoelectrochemistrpool pool working electrode
It is 100mW/cm after the irradiated measurement examination of luminous intensity2。
The experimental results showed that (being compared with reversible hydrogen electrode) under bias in 1.23V：Fe2O3The density of photocurrent of NR is
0.63mA/cm2；And ZrO2-Fe2O3The density of photocurrent of NT is 0.78mA/cm2.Thus it proves, ZrO2-Fe2O3NT compared to
Fe2O3NR has apparent advantage.
Embodiment 3
Step 1, high temperature resistant calcining iron oxide nanotube electrode is prepared：
(1) successively ultrasound 10 minutes in deionized water, acetone and ethanol solution successively by FTO electro-conductive glass, through go from
Sub- water is cleaned, and drying is spare；
(2) ferric trichloride and sodium nitrate precursor solution are prepared：2.16g ferric trichlorides and 6.8g sodium nitrate are weighed, is dissolved in
80mL water obtains the mixed solution of 0.1mol/L iron chloride and 1mol/L sodium nitrate；
(3) FTO substrates are put into above-mentioned precursor solution, 12h is reacted at 95 DEG C, elution, drying are obtained in FTO
The uniform FeOOH nanometer stick arrays grown in substrate；
(4) above-mentioned FeOOH samples are placed in the cavity of atomic layer deposition system, presoma used is four (ethyl first
Base amido) zirconium (IV) and water.Opening program is deposited, and the periodicity of deposition was 20 periods, was realized in FeOOH nanometer stick arrays
One layer of ZrO of coated with uniform2Film obtains the FeOOH-ZrO in FTO substrates2Nanometer stick array；
(5) by above-mentioned FeOOH-ZrO2Sample high-temperature roasting in air, using tube furnace, condition is：It 800 DEG C, keeps
10 minutes, Temperature fall obtained high temperature resistant calcining iron oxide nanotube electrode and (is denoted as ZrO2-Fe2O3NT)。
Step 2, Fe is prepared2O3Nanometer stick array：
(1) first synthesize FeOOH nanometer stick arrays, method is the same as (1) in step 1~(3) step；
(2) by above-mentioned FeOOH samples high-temperature roasting in air, using tube furnace, condition is：800 DEG C, kept for 10 points
Clock, Temperature fall obtain Fe2O3Nanometer stick array (is denoted as Fe2O3NR)。
Step 3, by ZrO2-Fe2O3NT and Fe2O3NR is used for photoelectrochemistrpool pool photolysis water hydrogen：
(1) respectively by ZrO2-Fe2O3NT and Fe2O3NR is used as working electrode, platinum plate electrode to electrode, silver/silver chlorate
Electrode is that reference electrode is assembled into photoelectrochemistrpool pool, carries out photoelectric property and photolysis water hydrogen performance test.Electrolyte is 1mol/
The KOH aqueous solutions of L, working electrode illuminating area are 1cm2；
(2) the xenon lamp collocation AM 1.5G optical filters of 300W are used to obtain simulated solar irradiation, at photoelectrochemistrpool pool working electrode
It is 100mW/cm after the irradiated measurement examination of luminous intensity2。
The experimental results showed that (being compared with reversible hydrogen electrode) under bias in 1.23V：Fe2O3The density of photocurrent of NR is
0.63mA/cm2；And ZrO2-Fe2O3The density of photocurrent of NT is 1.16mA/cm2.Thus it proves, ZrO2-Fe2O3NT compared to
Fe2O3NR has apparent advantage.
Embodiment 4
Step 1, high temperature resistant calcining iron oxide nanotube electrode is prepared：
(1) successively ultrasound 10 minutes in deionized water, acetone and ethanol solution successively by FTO electro-conductive glass, through go from
Sub- water is cleaned, and drying is spare；
(2) ferric trichloride and sodium nitrate precursor solution are prepared：2.16g ferric trichlorides and 6.8g sodium nitrate are weighed, is dissolved in
80mL water obtains the mixed solution of 0.1mol/L iron chloride and 1mol/L sodium nitrate；
(3) FTO substrates are put into above-mentioned precursor solution, 12h is reacted at 95 DEG C, elution, drying are obtained in FTO
The uniform FeOOH nanometer stick arrays grown in substrate；
(4) above-mentioned FeOOH samples are placed in the cavity of atomic layer deposition system, presoma used is four (ethyl first
Base amido) zirconium (IV) and water.Opening program is deposited, and the periodicity of deposition was 40 periods, was realized in FeOOH nanometer stick arrays
One layer of ZrO of coated with uniform2Film obtains the FeOOH-ZrO in FTO substrates2Nanometer stick array；
(5) by above-mentioned FeOOH-ZrO2Sample high-temperature roasting in air, using tube furnace, condition is：It 800 DEG C, keeps
10 minutes, Temperature fall obtained high temperature resistant calcining iron oxide nanotube electrode and (is denoted as ZrO2-Fe2O3NT)。
Step 2, Fe is prepared2O3Nanometer stick array：
(1) first synthesize FeOOH nanometer stick arrays, method is the same as (1) in step 1~(3) step；
(2) by above-mentioned FeOOH samples high-temperature roasting in air, using tube furnace, condition is：800 DEG C, kept for 10 points
Clock, Temperature fall obtain Fe2O3Nanometer stick array (is denoted as Fe2O3NR)。
Step 3, by ZrO2-Fe2O3NT and Fe2O3NR is used for photoelectrochemistrpool pool photolysis water hydrogen：
(1) respectively by ZrO2-Fe2O3NT and Fe2O3NR is used as working electrode, platinum plate electrode to electrode, silver/silver chlorate
Electrode is that reference electrode is assembled into photoelectrochemistrpool pool, carries out photoelectric property and photolysis water hydrogen performance test.Electrolyte is 1mol/
The KOH aqueous solutions of L, working electrode illuminating area are 1cm2；
(2) the xenon lamp collocation AM 1.5G optical filters of 300W are used to obtain simulated solar irradiation, at photoelectrochemistrpool pool working electrode
It is 100mW/cm after the irradiated measurement examination of luminous intensity2。
The experimental results showed that (being compared with reversible hydrogen electrode) under bias in 1.23V：Fe2O3The density of photocurrent of NR is
0.63mA/cm2；And ZrO2-Fe2O3The density of photocurrent of NT is 0.97mA/cm2.Thus it proves, ZrO2-Fe2O3NT compared to
Fe2O3NR has apparent advantage.
Embodiment 5
Step 1, high temperature resistant calcining iron oxide nanotube electrode is prepared：
(1) successively ultrasound 10 minutes in deionized water, acetone and ethanol solution successively by FTO electro-conductive glass, through go from
Sub- water is cleaned, and drying is spare；
(2) ferric trichloride and sodium nitrate precursor solution are prepared：2.16g ferric trichlorides and 6.8g sodium nitrate are weighed, is dissolved in
80mL water obtains the mixed solution of 0.1mol/L iron chloride and 1mol/L sodium nitrate；
(3) FTO substrates are put into above-mentioned precursor solution, 12h is reacted at 95 DEG C, elution, drying are obtained in FTO
The uniform FeOOH nanometer stick arrays grown in substrate；
(4) above-mentioned FeOOH samples are placed in the cavity of atomic layer deposition system, presoma used is four (ethyl first
Base amido) zirconium (IV) and water.Opening program is deposited, and the periodicity of deposition was 50 periods, was realized in FeOOH nanometer stick arrays
One layer of ZrO of coated with uniform2Film obtains the FeOOH-ZrO in FTO substrates2Nanometer stick array；
(5) by above-mentioned FeOOH-ZrO2Sample high-temperature roasting in air, using tube furnace, condition is：It 800 DEG C, keeps
10 minutes, Temperature fall obtained high temperature resistant calcining iron oxide nanotube electrode and (is denoted as ZrO2-Fe2O3NT)。
Step 2, Fe is prepared2O3Nanometer stick array：
(1) first synthesize FeOOH nanometer stick arrays, method is the same as (1) in step 1~(3) step；
(2) by above-mentioned FeOOH samples high-temperature roasting in air, using tube furnace, condition is：800 DEG C, kept for 10 points
Clock, Temperature fall obtain Fe2O3Nanometer stick array (is denoted as Fe2O3NR)。
Step 3, by ZrO2-Fe2O3NT and Fe2O3NR is used for photoelectrochemistrpool pool photolysis water hydrogen：
(1) respectively by ZrO2-Fe2O3NT and Fe2O3NR is used as working electrode, platinum plate electrode to electrode, silver/silver chlorate
Electrode is that reference electrode is assembled into photoelectrochemistrpool pool, carries out photoelectric property and photolysis water hydrogen performance test.Electrolyte is 1mol/
The KOH aqueous solutions of L, working electrode illuminating area are 1cm2；
(2) the xenon lamp collocation AM 1.5G optical filters of 300W are used to obtain simulated solar irradiation, at photoelectrochemistrpool pool working electrode
It is 100mW/cm after the irradiated measurement examination of luminous intensity2。
The experimental results showed that (being compared with reversible hydrogen electrode) under bias in 1.23V：Fe2O3The density of photocurrent of NR is
0.63mA/cm2；And ZrO2-Fe2O3The density of photocurrent of NT is 0.3mA/cm2.Thus it proves, works as ZrO2When deposition cycle is 50,
ZrO2-Fe2O3Apparent decline has occurred in NT activity.
Embodiment 6
Step 1, high temperature resistant calcining iron oxide nanotube electrode is prepared：
(1) successively ultrasound 10 minutes in deionized water, acetone and ethanol solution successively by FTO electro-conductive glass, through go from
Sub- water is cleaned, and drying is spare；
(2) ferric trichloride and sodium nitrate precursor solution are prepared：2.16g ferric trichlorides and 6.8g sodium nitrate are weighed, is dissolved in
80mL water obtains the mixed solution of 0.1mol/L iron chloride and 1mol/L sodium nitrate；
(3) FTO substrates are put into above-mentioned precursor solution, 6h is reacted at 95 DEG C, elution, drying are obtained in FTO bases
The uniform FeOOH nanometer stick arrays grown on bottom；
(4) above-mentioned FeOOH samples are placed in the cavity of atomic layer deposition system, presoma used is four (ethyl first
Base amido) zirconium (IV) and water.Opening program is deposited, and the periodicity of deposition was 30 periods, was realized in FeOOH nanometer stick arrays
One layer of ZrO of coated with uniform2Film obtains the FeOOH-ZrO in FTO substrates2Nanometer stick array；
(5) by above-mentioned FeOOH-ZrO2Sample high-temperature roasting in air, using tube furnace, condition is：It 800 DEG C, keeps
10 minutes, Temperature fall obtained high temperature resistant calcining iron oxide nanotube electrode and (is denoted as ZrO2-Fe2O3NT)。
Step 2, Fe is prepared2O3Nanometer stick array：
(1) first synthesize FeOOH nanometer stick arrays, method is the same as (1) in step 1~(3) step；
(2) by above-mentioned FeOOH samples high-temperature roasting in air, using tube furnace, condition is：800 DEG C, kept for 10 points
Clock, Temperature fall obtain Fe2O3Nanometer stick array (is denoted as Fe2O3NR)。
Step 3, by ZrO2-Fe2O3NT and Fe2O3NR is used for photoelectrochemistrpool pool photolysis water hydrogen：
(1) respectively by ZrO2-Fe2O3NT and Fe2O3NR is used as working electrode, platinum plate electrode to electrode, silver/silver chlorate
Electrode is that reference electrode is assembled into photoelectrochemistrpool pool, carries out photoelectric property and photolysis water hydrogen performance test.Electrolyte is 1mol/
The KOH aqueous solutions of L, working electrode illuminating area are 1cm2；
(2) the xenon lamp collocation AM 1.5G optical filters of 300W are used to obtain simulated solar irradiation, at photoelectrochemistrpool pool working electrode
It is 100mW/cm after the irradiated measurement examination of luminous intensity2。
The experimental results showed that the ZrO synthesized2-Fe2O3NT outer diameters are 100 ± 5nm, 20 ± 5nm of wall thickness, highly 220
±5nm.It (is compared with reversible hydrogen electrode) under bias in 1.23V：Fe2O3The density of photocurrent of NR is 0.63mA/cm2；And ZrO2-
Fe2O3The density of photocurrent of NT is 1.06mA/cm2.Thus it proves, ZrO2-Fe2O3NT is compared to Fe2O3NR has apparent advantage.
Embodiment 7
Step 1, high temperature resistant calcining iron oxide nanotube electrode is prepared：
(1) successively ultrasound 10 minutes in deionized water, acetone and ethanol solution successively by FTO electro-conductive glass, through go from
Sub- water is cleaned, and drying is spare；
(2) ferric trichloride and sodium nitrate precursor solution are prepared：2.16g ferric trichlorides and 6.8g sodium nitrate are weighed, is dissolved in
80mL water obtains the mixed solution of 0.1mol/L iron chloride and 1mol/L sodium nitrate；
(3) FTO substrates are put into above-mentioned precursor solution, 9h is reacted at 95 DEG C, elution, drying are obtained in FTO bases
The uniform FeOOH nanometer stick arrays grown on bottom；
(4) above-mentioned FeOOH samples are placed in the cavity of atomic layer deposition system, presoma used is four (ethyl first
Base amido) zirconium (IV) and water.Opening program is deposited, and the periodicity of deposition was 30 periods, was realized in FeOOH nanometer stick arrays
One layer of ZrO of coated with uniform2Film obtains the FeOOH-ZrO in FTO substrates2Nanometer stick array；
(5) by above-mentioned FeOOH-ZrO2Sample high-temperature roasting in air, using tube furnace, condition is：It 800 DEG C, keeps
10 minutes, Temperature fall obtained high temperature resistant calcining iron oxide nanotube electrode and (is denoted as ZrO2-Fe2O3NT)。
Step 2, Fe is prepared2O3Nanometer stick array：
(1) first synthesize FeOOH nanometer stick arrays, method is the same as (1) in step 1~(3) step；
(2) by above-mentioned FeOOH samples high-temperature roasting in air, using tube furnace, condition is：800 DEG C, kept for 10 points
Clock, Temperature fall obtain Fe2O3Nanometer stick array (is denoted as Fe2O3NR)。
Step 3, by ZrO2-Fe2O3NT and Fe2O3NR is used for photoelectrochemistrpool pool photolysis water hydrogen：
(1) respectively by ZrO2-Fe2O3NT and Fe2O3NR is used as working electrode, platinum plate electrode to electrode, silver/silver chlorate
Electrode is that reference electrode is assembled into photoelectrochemistrpool pool, carries out photoelectric property and photolysis water hydrogen performance test.Electrolyte is 1mol/
The KOH aqueous solutions of L, working electrode illuminating area are 1cm2；
(2) the xenon lamp collocation AM 1.5G optical filters of 300W are used to obtain simulated solar irradiation, at photoelectrochemistrpool pool working electrode
It is 100mW/cm after the irradiated measurement examination of luminous intensity2。
The experimental results showed that the ZrO synthesized2-Fe2O3NT outer diameters are 100 ± 5nm, 20 ± 5nm of wall thickness, highly 290
±5nm.It (is compared with reversible hydrogen electrode) under bias in 1.23V：Fe2O3The density of photocurrent of NR is 0.63mA/cm2；And ZrO2-
Fe2O3The density of photocurrent of NT is 1.35mA/cm2.Thus it proves, ZrO2-Fe2O3NT is compared to Fe2O3NR has apparent advantage.
The adjustment of technological parameter is carried out according to the content of present invention can prepare high temperature resistant calcining iron oxide nanotube electrode
And high temperature resistant calcining iron oxide nanotube electrode can show good photoelectric properties.Although above example combination attached drawing pair
The invention compares detailed description, but the invention is not limited to above-mentioned specific implementation mode, it should explanation,
In the case of not departing from core of the invention, any simple deformation is changed or can not spend wound in the case where the present invention enlightens
The various forms of transformation that the property made labour is made each fall within protection scope of the present invention.
Claims (8)
1. a kind of high temperature resistant calcining iron oxide nanotube electrode, it is characterised in that：By Fe of the vertical-growth on electro-conductive glass2O3
Nano-tube array and in Fe2O3In-stiu coating Fe around nanometer pipe outer wall2O3ZrO2Nanocrystal forms；The high temperature resistant roasting
Burn ferric oxide nano pipe electrode thickness and Fe2O3Nano-tube array is highly consistent, is 330~355nm；Fe2O3Outside nanotube
Diameter is 50~55nm, ZrO215~20nm of nano film thickness.
2. a kind of high temperature resistant calcining iron oxide nanotube electrode according to claim 1, it is characterised in that：The resistance to height
Warm calcining iron oxide nanotube electrode thickness and Fe2O3Nano-tube array is highly consistent, is 340~355nm.
3. a kind of preparation method of high temperature resistant calcining iron oxide nanotube electrode, it is characterised in that steps are as follows：
The sodium nitrate aqueous solution of the ferric trichloride of a concentration of 0.1~0.2mol/L and 1~2mol/L are mixed, will be mixed by step 1
The pH for closing solution is adjusted to 1.1~1.5, as the precursor solution for preparing FeOOH nanometer rods；
Electro-conductive glass substrate is put into the precursor solution described in step 1 by step 2, at 95~100 DEG C react 6~
12h, gained are the FeOOH nanometer stick arrays of the homoepitaxial in electro-conductive glass substrate；
FeOOH nanometer stick arrays described in step 2 are placed in the cavity of atomic layer deposition system and deposit by step 3,
Presoma used is four (ethyl-methyl amido) zirconiums (IV) and water, and number of deposition cycles is 10~50 periods, each deposition cycle
Depositing temperature be 150~300 DEG C, the time that is passed through of four (ethyl-methyl amido) zirconiums (IV) is 0.1~5s, corresponding carrier gas cleaning
Time is 5~20s, and the time that is passed through of presoma water is 0.01~1s, and corresponding carrier gas scavenging period is 10~30s；This step is real
One layer of ZrO of present FeOOH nanometer stick arrays coated with uniform2Film obtains the FeOOH-ZrO in electro-conductive glass substrate2It receives
Rice stick array；
Step 4, the temperature by the FeOOH-ZrO2 samples high-temperature roasting in air described in step 3, high-temperature roasting is 760
~840 DEG C, roasting time is to finally obtain ZrO in 6~14 minutes2-Fe2O3Nanotube is that the high temperature resistant calcining iron oxide is received
Mitron electrode.
4. a kind of preparation method of high temperature resistant calcining iron oxide nanotube electrode according to claim 3, it is characterised in that：
In step 1, the pH of mixed solution is adjusted to 1.2~1.3.
5. a kind of preparation method of high temperature resistant calcining iron oxide nanotube electrode according to claim 3, it is characterised in that：
Reaction time in step 2 is preferably 11~12h.
6. a kind of preparation method of high temperature resistant calcining iron oxide nanotube electrode according to claim 3, it is characterised in that：
Sedimentation cycle number in step 3 is preferably 10~40.
7. a kind of preparation method of high temperature resistant calcining iron oxide nanotube electrode according to claim 3, it is characterised in that：
The condition of high-temperature roasting described in step 4 is preferably 790~810 DEG C of calcination temperature, roasting time 9~11 minutes.
8. a kind of application of high temperature resistant calcining iron oxide nanotube electrode in optical electro-chemistry, it is characterised in that：The resistance to height
As working electrode, platinum plate electrode is used as to electrode warm calcining iron oxide nanotube electrode, and silver/silver chloride electrode is reference electricity
Three is assembled into photoelectrochemistrpool pool by pole, and electrolyte is the KOH aqueous solutions of 1~2mol/L, using the xenon lamp collocation AM of 300W
1.5G optical filters obtain simulated solar irradiation, and density of photocurrent is up to 0.7~1.5mA/cm when electrode activity is higher2, optical electro-chemistry
It is 100mW/cm after the irradiated measurement of luminous intensity tries at the working electrode of pond2。
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