CN107177859A - Pb3Nb4O13The preparation method of light anode material - Google Patents

Pb3Nb4O13The preparation method of light anode material Download PDF

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CN107177859A
CN107177859A CN201710351082.8A CN201710351082A CN107177859A CN 107177859 A CN107177859 A CN 107177859A CN 201710351082 A CN201710351082 A CN 201710351082A CN 107177859 A CN107177859 A CN 107177859A
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preparation
light anode
anode material
powder
time
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CN107177859B (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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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Hybrid Cells (AREA)

Abstract

The present invention proposes a kind of new light anode material Pb3Nb4O13Preparation method.The method is first with PbO and Nb2O5For raw material, Pb is prepared using solid reaction process3Nb4O13Powder, membrane electrode is prepared into using electrophoretic deposition by powder.And by Pb3Nb4O13Photoelectricity very thin films are calcined, and obtain the preferable electrode film of crystallinity.Pb3Nb4O13It is a kind of multi-element metal oxide, its position of energy band is appropriate for the decomposition of water across the conduction band of water and the position of valence band, its property stabilization, and with good photochemical properties in aqueous, and preparation method is simple, convenient operation.For Pb3Nb4O13Probe into, provide new catalysis material for the decomposition of water, alleviate the nervous situation of current environmental energy.

Description

Pb3Nb4O13The preparation method of light anode material
Technical field
The invention belongs to PhotoelectrochemicalTechnique Technique field, and in particular to a kind of new light anode material Pb3Nb4O13Preparation side Method.
Background technology
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 light anode material is the key for realizing optical electro-chemistry decomposition water large-scale application.It is used as reason The light anode semi-conducting material thought must be provided simultaneously with suitable band gap, conduction band valence-band level, effective carrier transport, stably Property the good and low feature of cost.However, in the light anode material found so far, above-mentioned want can be met simultaneously without one kind Ask.Therefore, the performance for improving existing semi-conducting material develops the new light anode new material gesture with application prospect must simultaneously OK.
Pb3Nb4O13It is a kind of multi-element metal oxide, its position of energy band is adapted to across the conduction band of water and the position of valence band Enter the decomposition of water-filling, its property stabilization, and with good photochemical properties in aqueous, in photocatalytic pollutant degradation There is good effect in field.So far, for Pb3Nb4O13The research of semi-conducting material seldom, light anode is used as it The research of the photoelectrochemical behaviour of material does not almost have.Therefore, studying or necessary for its potential performance.
The content of the invention
The present invention provides a kind of new light anode material Pb3Nb4O13Preparation method, this preparation method is simple, conveniently, condition Gently, extensive preparation is conducive to.
The technical solution adopted by the present invention is：A kind of Pb3Nb4O13The preparation method of light anode material, including it is following Step：
1）Measure appropriate PbO and Nb2O5It is mixed in ethanol, certain time is ground in ball mill, after is cleaned with ethanol simultaneously Drying, by the powder high annealing certain time after drying, is cooled to room temperature；
2）By the powder regrinding after annealing, high-temperature process for a period of time, is cooled to room temperature again after grinding, obtains Pb3Nb4O13Powder.
3）By appropriate Pb3Nb4O13Powder sample is scattered in containing I2Solution A in, obtain electrophoresis under the concussion of ultrasonic wave The suspension of deposition.By the transparent conducting glass of two area equations（FTO）Be parallel to each other immersion above suspension face-to-face, and Apply certain DC voltage between two electrodes, the time of depositing and setting, cut off electric current, electrode is taken out from suspension, Dried under room temperature condition and obtain Pb in Muffle kiln roasting3Nb4O13Photoelectricity very thin films；
Described step 1）The material ratio of middle ball milling is 60:1, solid-to-liquid ratio is 1:2, Ball-milling Time is 14h.
Described step 1）Middle annealing temperature be 600 degree of times be 6h.
Described step 2）The temperature of high temperature processing is 850 degree, and the time is 4h.
Described step 3）In contain I2Solution A be the mixed solution of acetone and water, its ratio is 25:1.
Described step 3）Middle DC voltage is 15V, and the time is 1-5min.
The invention has the advantages that：
Pb3Nb4O13It is a kind of non-metal N type semiconductor, due to that with good optical characteristics, can be less than with absorbing wavelength 420nm visible ray, makes it cause the concern of people in photocatalysis field, and its energy gap is 2.9eV, conduction band and valence band location Across the conduction band valence band location of water, the potential value with decomposition water, and preparation method is simple, convenient operation.For point of water Solution provides new catalysis material, alleviates the nervous situation of current environmental energy.
Brief description of the drawings
The Pb that Fig. 1 obtains for ball milling in embodiment 13Nb4O13The XRD of powder.
Fig. 2 is the Pb of different sintering temperatures in embodiment 13Nb4O13The XRD of film.
Fig. 3 is the Pb obtained under different sintering temperatures in embodiment 13Nb4O13The SEM figures of film.
Fig. 4 is the Pb obtained under different sintering temperatures in embodiment 23Nb4O13The comparison diagram of the photoelectric current of film.
Fig. 5 is the Pb obtained under different sintering temperatures in embodiment 23Nb4O13The comparison diagram of the impedance spectrum of film.
Fig. 6 is Pb in embodiment 23Nb4O13The quantum efficiency figure of film.
Embodiment
The Pb of embodiment 13Nb4O13Light anode material
（One）Pb3Nb4O13The preparation of powder：
1）Take 7.5mmol PbO and 5mmol Nb2O5It is mixed in ethanol, its solid-liquid mass ratio ratio is 1：2, it is evenly stirred until In ball grinder, mill ball is 265g in tank；
2）Start ball mill, settings rotating speed is 200 r/min, grind 14h, closing power supply after being cleaned with ethanol and is dried, will dried Powder after dry 600 degree 6h that anneal in Muffle furnace, are cooled to room temperature；
3）Powder after annealing is repeated 1 again）, 2）The step of be ground, 850 degree of 4h are calcined after grinding again, are cooled to Room temperature, obtains Pb3Nb4O13Powder.
The powder that step 3 is obtained carries out XRD tests, as a result as shown in figure 1, as can be seen from the figure the powder is Pb3Nb4O13, with good crystallinity.
（Two）Pb3Nb4O13The preparation of electrode film：
1）Take 10mg I2In the mixed solution for being placed in deionized water and acetone（The volume ratio of water and acetone is 1:25）, seal super Sound 30min is uniformly dispersed to solution；
2）By 1）In obtain adding 0.1g Pb in uniform dispersion liquid3Nb4O13Powder, seals ultrasound 1h, obtains electrophoretic deposition and hangs Supernatant liquid；
3）By the transparent conducting glass of two area equations（FTO）Be parallel to each other immersion 2 face-to-face）In obtained suspension, and Apply 15V DC voltage between two electrodes, deposit 3min；
4）Cut off electric current, electrode is taken out from suspension, dry at ambient temperature and in Muffle kiln roasting 400 degree obtain Pb3Nb4O13Photoelectricity very thin films, labeled as Pb3Nb4O13-400
5）Above step is repeated, only by step 4）In sintering temperature be changed to 450 degree and 500 degree two obtained film samples respectively Product are respectively labeled as Pb3Nb4O13- 450, Pb3Nb4O13-500.
Three samples that step is obtained carry out XRD tests, as a result as shown in Fig. 2 as can be seen from the figure with sintering temperature Increase, the enhancing of the crystallinity of sample；Again by sample carry out SEM tests, as a result as shown in figure 3, as can be seen from the figure with Temperature increases, and film surface porosity step-down, film is finer and close.
The Pb of embodiment 23Nb4O13The application of electrode film
The Pb respectively prepared by embodiment 13Nb4O13-400、Pb3Nb4O13- 400 and Pb3Nb4O13- 400 light anodes carry out photoelectricity The a series of photoelectrochemical behaviour test such as stream, impedance and quantum efficiency.
All electrochemistry experiment test process are all in the electrochemical workstation of three-electrode system（Princeton Applied Research 2273）It is middle to carry out.Sample thin film is as working electrode, and platinized platinum is that Ag/AgCl is reference electrode to electrode, electrolysis Liquid is 0.5M sodium sulphate, and sample light irradiation area is 1 cm2。
Photoelectricity current test：Light source is 300W xenon lamps, is biased as 1.18v vs. VRHE, result is measured as shown in figure 4, result It has been shown that, influence of the sintering temperature to photoelectric current, with the rise of temperature, photoelectric current also increases therewith.
Electrochemical impedance spectroscopy（EIS）Test：Fixed voltage is 0V vs.Voc, frequency range is 0.1 ~ 105Hz.Measure knot Fruit is as shown in figure 5, sintering temperature is higher, and impedance is smaller, wherein, the impedance value for supporting Co-Pi sample 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.Utilize formula：
Wherein, I is density of photocurrent（Unit：µA）, λ is incident monochromatic wavelength (nm), and P is incident intensity（Unit：µW）.It is logical Cross the value for calculating quantum efficiency, as a result as shown in fig. 6, wavelength be 390nm monochromatic light exposures under quantum efficiency highest.

Claims (7)

1. a kind of Pb3Nb4O13The preparation method of light anode material, it is characterised in that including following steps：
1）Measure appropriate PbO and Nb2O5It is mixed in ethanol, certain time is ground in ball mill, after is cleaned with ethanol simultaneously Drying, by the powder high annealing certain time after drying, is cooled to room temperature；
2）By the powder regrinding after annealing, high-temperature process for a period of time, is cooled to room temperature again after grinding, obtains Pb3Nb4O13Powder；
3）By appropriate Pb3Nb4O13Powder sample is scattered in containing I2Solution A in, obtain electrophoretic deposition under the concussion of ultrasonic wave Suspension.
2. by the transparent conducting glass of two area equations（FTO）Be parallel to each other immersion above suspension face-to-face, and in two electricity Interpolar applies certain DC voltage, the time of depositing and setting, cuts off electric current, electrode is taken out from suspension, in room temperature bar Dried under part and obtain Pb in Muffle kiln roasting3Nb4O13Photoelectricity very thin films.
3. preparation method according to claim 1, it is characterised in that step 1）The material ratio of middle ball milling is 60:1, solid-liquid Than for 1:2, Ball-milling Time is 14h.
4. Pb according to claim 13Nb4O13The preparation method of light anode material, it is characterised in that step 1）Middle annealing temperature Degree be 600 degree of times be 6h.
5. Pb according to claim 13Nb4O13The preparation method of light anode material, it is characterised in that step 2）At high temperature The temperature of reason is 850 degree, and the time is 4h.
6. Pb according to claim 13Nb4O13The preparation method of light anode material, it is characterised in that step 3）In contain I2 Solution A be the mixed solution of acetone and water, its ratio is 25:1.
7. Pb according to claim 13Nb4O13The preparation method of light anode material, it is characterised in that step 3）Middle direct current Press as 15V, the time is 1-5min.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107994120A (en) * 2017-11-22 2018-05-04 辽宁大学 Sn2Nb2O7Light anode material and Sn2Nb2O7Photoelectricity very thin films
CN108531954A (en) * 2018-04-17 2018-09-14 陕西科技大学 The electrochemical preparation method of polyaniline/two-dimensional layer carbonization titanium composite material
CN108611660A (en) * 2018-05-10 2018-10-02 辽宁大学 High-photoelectric transformation efficiency Bi2MoO6Light anode and its preparation method and application
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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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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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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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107994120A (en) * 2017-11-22 2018-05-04 辽宁大学 Sn2Nb2O7Light anode material and Sn2Nb2O7Photoelectricity very thin films
CN107994120B (en) * 2017-11-22 2024-05-07 辽宁大学 Sn2Nb2O7Photoanode material and Sn2Nb2O7Photoelectrode film
CN108531954A (en) * 2018-04-17 2018-09-14 陕西科技大学 The electrochemical preparation method of polyaniline/two-dimensional layer carbonization titanium composite material
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
CN108611660A (en) * 2018-05-10 2018-10-02 辽宁大学 High-photoelectric transformation efficiency Bi2MoO6Light anode and its preparation method and application
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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