CN107177859B - Pb3Nb4O13The preparation method of optical anode material - Google Patents

Pb3Nb4O13The preparation method of optical anode material Download PDF

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CN107177859B
CN107177859B CN201710351082.8A CN201710351082A CN107177859B CN 107177859 B CN107177859 B CN 107177859B CN 201710351082 A CN201710351082 A CN 201710351082A CN 107177859 B CN107177859 B CN 107177859B
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powder
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anode material
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CN107177859A (en
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范晓星
田莉
孔令茹
王洪亮
韩东远
刘京
韩宇
王绩伟
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Liaoning University
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/50—Processes
    • C25B1/55—Photoelectrolysis
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/02—Electrophoretic coating characterised by the process with inorganic material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention proposes a kind of new optical anode material Pb3Nb4O13Preparation method.The method is first with PbO and Nb2O5For raw material, Pb is prepared using solid reaction process3Nb4O13Powder is prepared into membrane electrode using electrophoretic deposition by powder.And by Pb3Nb4O13The roasting of photoelectricity very thin films, obtains the preferable electrode film of crystallinity.Pb3Nb4O13It is a kind of multi-element metal oxide, position of energy band is appropriate for the decomposition of water across the conduction band of water and the position of valence band, and property is stablized in aqueous solution, and has good photochemical properties, and preparation method is simple, facilitates operation.For Pb3Nb4O13Probe into, provide new catalysis material for the decomposition of water, alleviate the situation of current environmental energy anxiety.

Description

Pb3Nb4O13The preparation method of optical anode material
Technical field
The invention belongs to PhotoelectrochemicalTechnique Technique fields, and in particular to a kind of new optical anode material Pb3Nb4O13Preparation side Method.
Background technique
Optical electro-chemistry hydrogen production by water decomposition converts solar energy into storable chemical energy, is to solve environment and energy in 21st century The main means of source problem.The exploitation of optical anode material is the key that realize that optical electro-chemistry decomposes water large-scale application.As reason The light anode semiconductor material thought must be provided simultaneously with suitable band gap, conduction band valence-band level, effective carrier transport, stabilization Property it is good and at low cost the features such as.However, above-mentioned want can be met simultaneously without a kind of in the optical anode material found so far It asks.Therefore, improve the performance of existing semiconductor material while the new light anode new material gesture with application prospect of development is must Row.
Pb3Nb4O13It is a kind of multi-element metal oxide, position of energy band is suitble to across the conduction band of water and the position of valence band The decomposition of water is carried out, property is stablized in aqueous solution, and has good photochemical properties, in photocatalytic pollutant degradation There is good effect in field.So far, for Pb3Nb4O13The research of semiconductor material is seldom, for it as light anode The research of the photoelectrochemical behaviour of material almost without.Therefore, for its potential performance research or it is necessary.
Summary of the invention
The present invention provides a kind of new optical anode material Pb3Nb4O13Preparation method, this preparation method is simple, conveniently, condition Mildly, be conducive to large scale preparation.
A kind of the technical solution adopted by the present invention are as follows: Pb3Nb4O13The preparation method of optical anode material, including it is following Step:
1) suitable PbO and Nb is measured2O5It is mixed in ethyl alcohol, grinds certain time in the ball mill, cleaned with ethyl alcohol It afterwards and dries, the powder high annealing certain time after drying is cooled to room temperature；
2) powder after annealing is regrind, high-temperature process for a period of time, is cooled to room temperature again after grinding, is obtained Pb3Nb4O13Powder.
3) by suitable Pb3Nb4O13Powder sample is scattered in containing I2Solution A in, obtain electrophoresis under the concussion of ultrasonic wave The suspension of deposition.The FTO of two area equations is parallel to each other face-to-face and immerses the above suspension, and is applied between two electrodes Certain DC voltage, the time of depositing and setting cut off electric current, electrode are taken out from suspension, is dried at room temperature And Pb is obtained in Muffle kiln roasting3Nb4O13Photoelectricity very thin films；
The quality of material ratio of ball milling is 60:1, solid-liquid mass ratio 1:2, Ball-milling Time 14h in the step 1).
It is 6h that annealing temperature, which is 600 degree of times, in the step 1).
The temperature of step 2) the high temperature processing is 850 degree, time 4h.
Contain I in the step 3)2Solution A be acetone and water mixed solution, volume ratio 25:1.
DC voltage is 15V, time 1-5min in the step 3).
The invention has the following advantages:
Pb3Nb4O13It is a kind of non-metal N type semiconductor, due to wavelength can be absorbed and be less than with good optical characteristics The visible light of 420nm makes it cause the concern of people, forbidden bandwidth 2.9eV, conduction band and valence band location in photocatalysis field Across the conduction band valence band location of water, there is the potential value for decomposing water, and preparation method is simple, facilitates operation.For point of water Solution provides new catalysis material, alleviates the situation of current environmental energy anxiety.
Detailed description of the invention
Fig. 1 is the Pb that ball milling obtains in embodiment 13Nb4O13The XRD diagram of powder.
Fig. 2 is the Pb of different maturing temperatures in embodiment 13Nb4O13The XRD diagram of film.
Fig. 3 is the Pb obtained under different maturing temperatures in embodiment 13Nb4O13The SEM of film schemes.
Fig. 4 is the Pb obtained under different maturing temperatures in embodiment 23Nb4O13The comparison diagram of the photoelectric current of film.
Fig. 5 is the Pb obtained under different maturing temperatures in embodiment 23Nb4O13The comparison diagram of the impedance spectrum of film.
Fig. 6 is Pb in embodiment 23Nb4O13The quantum efficiency figure of film.
Specific embodiment
1 Pb of embodiment3Nb4O13Optical anode material
(1) Pb3Nb4O13The preparation of powder:
1) Nb of the PbO and 5mmol of 7.5mmol are taken2O5It is mixed in ethyl alcohol, solid-liquid mass ratio 1:2 is stirred evenly As in ball grinder, mill ball is 265g in tank；
2) starting ball mill, setting revolving speed is 200 r/min, 14h ground, power supply is closed, after being cleaned with ethyl alcohol and dries, By the powder after drying in Muffle furnace 600 degree of annealing 6h, be cooled to room temperature；
3) by the powder after annealing again repeat 1), 2) the step of ground, 850 degree of 4h are calcined after grinding again, it is cold But to room temperature, Pb is obtained3Nb4O13Powder.
The powder that step 3 is obtained carries out XRD test, as a result as shown in Figure 1, as can be seen from the figure the powder is Pb3Nb4O13, there is good crystallinity.
(2) Pb3Nb4O13The preparation of electrode film:
1) 10mg I is taken2It is placed in the mixed solution of deionized water and acetone (volume ratio of water and acetone is 1:25), it is close Envelope ultrasound 30min is uniformly dispersed to solution；
2) 1) it will obtain in that 0.1g Pb is added in uniform dispersion liquid3Nb4O13Powder seals ultrasound 1h, and it is heavy to obtain electrophoresis Product suspension；
3) FTO of two area equations is parallel to each other immersion 2 face-to-face) obtained in suspension, and between two electrodes Apply the DC voltage of 15V, deposits 3min；
4) electric current is cut off, electrode is taken out from suspension, is dried at room temperature and at 400 degree of Muffle kiln roasting Obtain Pb3Nb4O13Photoelectricity very thin films are labeled as Pb3Nb4O13-400
5) above step is repeated, it is thin that the maturing temperature in step 4) is only changed to 450 degree and 500 degree two obtained respectively Membrane sample is respectively labeled as Pb3Nb4O13- 450, Pb3Nb4O13-500.
Step three obtained sample is subjected to XRD test, as a result as shown in Fig. 2, as can be seen from the figure with roasting Temperature increases, the crystallinity enhancing of sample；Sample is subjected to SEM test again, as a result as shown in figure 3, as can be seen from the figure With increasing for temperature, film surface porosity is lower, and film is finer and close.
2 Pb of embodiment3Nb4O13The application of electrode film
The Pb respectively prepared by embodiment 13Nb4O13-400、Pb3Nb4O13- 450 and Pb3Nb4O13- 500 light anodes carry out light The a series of photoelectrochemical behaviour test such as electric current, impedance and quantum efficiency.
All electrochemistry experiment test process are all in the electrochemical workstation of three-electrode system (Princeton Applied Research 2273) in carry out.Sample thin film is to electrode as working electrode, platinized platinum, and Ag/AgCl is reference electrode, electrolysis Liquid is 0.5M sodium sulphate, and sample photoirradiated surface product is 1 cm2。
Photoelectricity current test: light source is 300W xenon lamp, and bias is 1.18v vs. VRHE, result is measured as shown in figure 4, result It has been shown that, influence of the maturing temperature to photoelectric current, as the temperature rises, photoelectric current also increases with it.
Electrochemical impedance spectroscopy (EIS) test: fixed voltage is 0V vs.Voc, frequency range is 0.1 ~ 105Hz.Measure knot For fruit as shown in figure 5, maturing temperature is higher, impedance is smaller, wherein the impedance value for supporting the sample of Co-Pi is minimum；
Quantum efficiency (IPCE) test: choose multiple wavelength (380nm, 390nm, 410nm, 420nm, 430nm, 450nm, 460nm, 490nm) monochromatic light exposure sample, measure its bias be 1.18V vs. VRHEWhen photoelectric current.Benefit With formula:
Wherein, I is density of photocurrent (unit: μ A), and λ is incident monochromatic wavelength (nm), and P is incident intensity (unit: μ W).By the way that the value of quantum efficiency is calculated, as a result as shown in fig. 6, wavelength be 390nm monochromatic light exposure under quantum efficiency Highest.

Claims (3)

1. a kind of Pb3Nb4O13The preparation method of optical anode material, which is characterized in that including the following steps:
1) suitable PbO and Nb is measured2O5It is mixed in ethyl alcohol, solid-liquid mass ratio 1:2, grinds a timing in the ball mill Between, the material ratio of ball milling is 60:1, and Ball-milling Time 14h after being cleaned with ethyl alcohol and is dried, by the powder high annealing after drying Certain time is cooled to room temperature；
2) powder after annealing is regrind, high-temperature process for a period of time, is cooled to room temperature again after grinding, is obtained Pb3Nb4O13Powder；
3) by suitable Pb3Nb4O13Powder sample is scattered in containing I2Solution A in, obtain electrophoretic deposition under the concussion of ultrasonic wave Suspension；Contain I2Solution A be acetone and water mixed solution, volume ratio 25:1；
4) FTO of two area equations is parallel to each other face-to-face and immerses the above suspension, and applied centainly between two electrodes DC voltage 15V, the time 1-5min of depositing and setting cut off electric current, electrode are taken out from suspension, is dried in the air at room temperature Dry doubling obtains Pb in Muffle kiln roasting3Nb4O13Photoelectricity very thin films.
2. Pb according to claim 13Nb4O13The preparation method of optical anode material, which is characterized in that temperature of annealing in step 1) It is 6h that degree, which is 600 degree of times,.
3. Pb according to claim 13Nb4O13The preparation method of optical anode material, which is characterized in that at step 2 high temperature The temperature of reason is 850 degree, time 4h.
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CN107994120B (en) * 2017-11-22 2024-05-07 辽宁大学 Sn2Nb2O7Photoanode material and Sn2Nb2O7Photoelectrode film
CN108531954B (en) * 2018-04-17 2020-06-02 陕西科技大学 Electrochemical preparation method of polyaniline/two-dimensional layered titanium carbide composite material
CN108611660B (en) * 2018-05-10 2020-04-10 辽宁大学 Bi with high photoelectric conversion efficiency2MoO6Photo-anode and preparation method and application thereof
CN114507877A (en) * 2022-02-23 2022-05-17 辽宁大学 Preparation method and application of photoelectrode film with graphite carbon nitride as substrate material

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CN102775185A (en) * 2012-07-26 2012-11-14 天津大学 Dielectric adjustable lead niobate thin film material
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Patent Citations (4)

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TW512137B (en) * 1998-12-24 2002-12-01 Tzung-Shin Liu Low-temperature crystallization of ceramic films by high-pressure processing
CN101154509A (en) * 2006-07-05 2008-04-02 通用电气公司 Contact material, device including contact material, and method of making
CN102775185A (en) * 2012-07-26 2012-11-14 天津大学 Dielectric adjustable lead niobate thin film material
CN104399450A (en) * 2014-11-25 2015-03-11 辽宁大学 Preparation method and application of large specific surface area niobate photocatalyst

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