CN102995053B - Method for preparing LaTiO2N high-efficiency photoelectrode material - Google Patents

Method for preparing LaTiO2N high-efficiency photoelectrode material Download PDF

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CN102995053B
CN102995053B CN201210499022.8A CN201210499022A CN102995053B CN 102995053 B CN102995053 B CN 102995053B CN 201210499022 A CN201210499022 A CN 201210499022A CN 102995053 B CN102995053 B CN 102995053B
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latio
optoelectronic pole
preparing
latio2n
particle
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CN102995053A (en
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李朝升
冯建勇
吕浩
方涛
祝梅
邹志刚
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Nanjing University
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Nanjing University
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    • 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

Abstract

The invention relates to a method for preparing a LaTiO2N high-efficiency photoelectrode material. The method comprises the following steps of: preparing a precursor La2Ti2O7 of LaTiO2N by using a solid-phase reaction method, and weighing La2O3 and TiO2 according to a molar rate of La to Ti of the La2Ti2O7; uniformly mixing and sufficiently grinding the La2O3 and TiO2; calcining the uniformly mixed raw material for 6-20h at the temperature of 800-1000 DEG C, then cooling to room temperature, grinding and calcining the grinded raw material for 6-20h again at the temperature of 1100-1400DEG C; depositing the LaTiO2N particles on a conductive glass (FTO (Fluorine Doped Tin Oxide)) substrate by using an electrophoretic deposition method, and drying in the air to obtain a LaTiO2N particle film; and then dropwise adding a TiC14 methanol solution on the prepared LaTiO2N particle film, and carrying out thermal treatment for 10-60min at 300-700 DEG C in an ammonia atmosphere to obtain the LaTiO2N photoelectrode.

Description

The method of preparing lanthanium titanate oxynitride efficiency light electrode material
Technical field
The present invention relates to a kind of lanthanium titanate oxynitride (LaTiO for preparing 2n) method of efficiency light electrode material.
Background technology
The world today runs into energy shortage and environmental pollution two hang-ups, is restricting the mankind's Sustainable development.Developing clean renewable energy source is the task of top priority.It is nearly ten thousand times that the mankind consume total energy at present year that the sun is irradiated to tellurian energy for 1 year.From long term growth, in the situation that fossil energy faces exhausted and environment severe exacerbation, sun power, because of cleanliness without any pollution, the advantage such as widely distributed, inexhaustible, nexhaustible, will be played the part of important role in following energy structure.Yet sun power has the shortcomings such as energy density is low, dispersiveness is strong, unstable, discontinuous, and we are still lacked so far to its efficient, low-cost, extensive effective means of utilizing.Photoelectrochemical cell can utilize decomposing water with solar energy, and that by the solar energy converting of low energy densities, be high-energy-density, that easily store, cleaning chemistry Hydrogen Energy are hopeful to play a significant role in solution energy problem, therefore receive the concern of numerous various countries.Using the key of photoelectrochemical cell hydrogen production by water decomposition is to find efficient stable optoelectronic pole material.Up to the present, can meet the optoelectronic pole material of efficient and these two conditions of light stability few simultaneously.
Lanthanium titanate oxynitride (LaTiO 2n) can absorb the visible ray [A.Kasahara of 600nm, K.Nukumizu, G.Hitoki, J.N.Kondo, M.Hara, H.Kobayashi, K.Domen, J.Phys.Chem.A, 106,6750-6753 (2002)], the efficiency of its theoretical solar energy converting Hydrogen Energy is up to 16%, but the efficiency of actual solar energy converting Hydrogen Energy is very low.
Summary of the invention
The object of the invention is, propose a kind of high quality lanthanium titanate oxynitride (LaTiO for preparing 2n) method of efficiency light electrode material, makes LaTiO 2n solar energy converting Hydrogen Energy efficiency increases substantially, and promotes the practical application of solar hydrogen making.
Technical scheme of the present invention is efficiency light electrode material LaTiO 2the preparation method of N, comprises the steps:
(1) utilize solid reaction process to prepare LaTiO 2the presoma La of N 2ti 2o 7, according to La 2ti 2o 7la and the molar weight proportioning of Ti take La 2o 3and TiO 2;
(2) raw material step (1) being taken, mixes and fully grinds;
(3) in solid reaction process, by the raw material mixing, 800 ° of C ~ 1000, ° C calcines 6h ~ 20h, is then cooled to room temperature, and after grinding, 1100 ° of C ~ 1400, ° C calcines 10h again;
(4) the cooling rear grinding of product that step (3) obtains, obtains La 2ti 2o 7particle;
(5) step (4) is prepared to La 2ti 2o 7at NH 3in atmosphere, 600 ° of C ~ 1000 ° C thermal treatment 15h, obtain LaTiO 2n particle;
(6) LaTiO that utilizes electrophoretic deposition prepared by step (5) 2n particle deposition, at conductive glass, at air drying, is prepared LaTiO 2n membrana granulosa;
(7) LaTiO preparing in step (6) 2on N membrana granulosa, splash into TiCl 4methanol solution, then, by its ammonia atmosphere lower 300 ° of C ~ 700 ° C thermal treatment 10 minutes ~ 60 minutes, has obtained LaTiO 2n optoelectronic pole.
(8) LaTiO preparing in step (7) 2on the surface of N optoelectronic pole, support Co 3o 4eelctro-catalyst, makes the LaTiO preparing 2n optoelectronic pole has high-efficiency solar converts hydrogen energy efficiency.Support Co 3o 4the concrete technology of eelctro-catalyst is as follows: with NaOH solution, splash into Co 2+the aqueous solution, form Co (OH) 2colloid, then by LaTiO 2n optoelectronic pole immerses in this colloid, floods 10 minutes ~ 120 minutes; Take out again LaTiO 2n optoelectronic pole, water rinses LaTiO 2n optoelectronic pole, finally ° C sintering 1h 200 ° of C ~ 400, obtains Co 3o 4finishing LaTiO 2n optoelectronic pole.
Step (6) swimming deposition step: during electrophoresis, electrolytic solution adopts the acetone soln of iodine, by LaTiO 2n particulate material is suspended in this electrolytic solution; Anode and negative electrode all adopt conductive glass, and negative electrode is parallel with anode, and the conductive glass of negative electrode and anode 2/3 partly immerses the acetone soln of iodine, and the direct current that employing voltage is 10V ~ 40V is by the LaTiO suspending in electrolytic solution 2n particle deposition, at the conductive glass of negative electrode, obtains LaTiO 2n optoelectronic pole.
The invention has the beneficial effects as follows: the lanthanium titanate oxynitride (LaTiO that adopts present method to prepare 2n) efficiency light electrode material, makes LaTiO 2n solar energy converting Hydrogen Energy efficiency increases substantially, (AM 1.5G, 100mW cm under simulated solar irradiation -2) photoelectric current surpass 4.2mA/cm 2(bias voltage is 1.5V), corresponding solar energy converting Hydrogen Energy efficiency is 5.2%.
Accompanying drawing explanation
Fig. 1 is the LaTiO preparing under different condition 2the X ray diffracting spectrum of N;
Fig. 2 is the LaTiO preparing under different condition 2the optical absorption map of N;
Fig. 3 is LaTiO 2the conversion quantum efficiency of N optoelectronic pole under different bias voltages;
Fig. 4 is LaTiO 2the electromicroscopic photograph of N optoelectronic pole;
Fig. 5 is LaTiO 2the photoelectricity flow graph of N optoelectronic pole under simulated solar irradiation.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the invention will be further described.
Efficiency light electrode material LaTiO 2the preparation method of N comprises the steps:
(1) utilize solid reaction process to prepare LaTiO 2the presoma La of N 2ti 2o 7, according to La 2ti 2o 7la and the molar weight proportioning of Ti take La 2o 3and TiO 2;
(2), by above-mentioned raw materials, mix and fully grind; Be ground to the particle diameter that is mainly distributed in 1 micron ~ 4 microns;
(3), in solid reaction process, the raw material mixing is calcined to 6h, 10h, 12h, 20h at 800 ° of C, 900 or 1000 ° of C, and calcining under normal air condition, also can under weak vacuum condition, calcine, be then cooled to room temperature.Carry out second step grinding, second step grinds also to being mainly distributed in the particle diameter of 1 micron ~ 4 microns; After grinding, at 1100 ° of C, 1250 ° of C or 1400 ° of C, calcine 10h again.The sample crystallinity of 1250 ° of C sintering is best;
(4) the cooling rear grinding of product that step (3) obtains, obtains La 2ti 2o 7particle; Be ground to the particle diameter that particle is mainly distributed in 1 micron ~ 4 microns; (the more than 85% of quality);
(5) step (4) is prepared to La 2ti 2o 7at NH 3in atmosphere, 600 ° of C, 700 ° of C, 850 ° of C, 950 ° of C, 1000 ° of C thermal treatment 15h, obtain LaTiO 2n particle, ammonia flow is at 20ml/min ~ 1000ml/min, result shows 950 ° of C(200ml/min, 15h) synthetic properties of sample is best;
(6) utilize electrophoretic deposition by the synthetic LaTiO of step (5) 2n particle deposition, at conductive glass, at air drying, is prepared LaTiO 2n membrana granulosa.The concrete technology of electrophoretic deposition is that electrolytic solution adopts acetone soln containing iodine (solvent acetone is 50ml; Solute iodine is 10mg), by 40mg LaTiO 2n is suspended in this electrolytic solution; It is 3cm that anode and negative electrode all adopt area 2conductive glass (F-doped SnO 2), negative electrode is parallel with anode, and the conductive glass of negative electrode and anode 2/3 partly immerses the acetone soln of iodine, and employing voltage is that the direct current of 10V, 30V or 40V is by the LaTiO suspending in electrolytic solution 2n particle deposition, at the conductive glass (depositing time is 2 minutes) of negative electrode, obtains LaTiO 2n optoelectronic pole.
(7) LaTiO preparing in step (6) 2on N membrana granulosa, splash into TiCl 4methanol solution, by (500ml/min) under its ammonia atmosphere 500 ° of C thermal treatments 30 minutes, obtains the interconnected LaTiO of particle 2n optoelectronic pole.
(8) LaTiO preparing in step (7) 2on the surface of N optoelectronic pole, support Co 3o 4eelctro-catalyst, makes the LaTiO preparing 2n optoelectronic pole has high-efficiency solar converts hydrogen energy efficiency.Support Co 3o 4the concrete technology of eelctro-catalyst is as follows: with NaOH solution, splash into containing Co 2+the aqueous solution, form Co (OH) 2colloid, then by LaTiO 2n optoelectronic pole immerses this colloid, floods 10 minutes; Take out again LaTiO 2n optoelectronic pole, water rinses LaTiO 2n optoelectronic pole, finally at 300 ° of C sintering 1h, obtains Co 3o 4finishing LaTiO 2n optoelectronic pole.
Fig. 1 is La prepared by solid sintering technology (1250 ° of C) 2ti 2o 7with processing (950 ° of C, 200ml/min) resulting LaTiO under ammonia atmosphere 2the X ray diffracting spectrum of N sample.From X ray diffracting spectrum, can find out: synthetic La 2ti 2o 7and LaTiO 2n sample is all pure phase, does not have dephasign to occur.
Fig. 2 has provided La prepared by solid sintering technology (1250 ° of C) 2ti 2o 7under ammonia atmosphere, process (950 ° of C, 200ml/min) resulting LaTiO 2the optical absorption spectra of N sample.LaTiO 2n sample optical absorption edge reaches 600nm, and 600nm has obvious hangover later, and this hangover may be from Ti 3+the photoabsorption of defect.
Fig. 3 has provided La prepared by solid sintering technology (1250 ° of C) 2ti 2o 7under ammonia atmosphere, process (950 ° of C, 200ml/min) resulting LaTiO 2n(LTON SSR 1250) the light action spectrum (quantum yield IPCE with wavelength change curve) of sample under different bias voltages.Under 1.23V bias voltage (reversible hydrogen electrode), support Co 3o 4the LaTiO of catalyzer 2the quantum yield of N within the scope of 380nm ~ 560nm reaches 25% left and right.
Fig. 4 has provided La prepared by solid sintering technology (1250 ° of C) 2ti 2o 7under ammonia atmosphere, process (950 ° of C, 200ml/min) resulting LaTiO 2the shape appearance figure of N sample.Illustration is wherein LaTiO 2the selected diffraction figure of N.Can find out LaTiO 2n has good crystallinity, and particle presents the diffraction pattern of monocrystalline.
Fig. 5 has provided La prepared by solid sintering technology (1250 ° of C) 2ti 2o 7under ammonia atmosphere, process (950 ° of C, 200ml/min) resulting LaTiO 2n sample is (AM 1.5G, 100mW cm under simulated solar irradiation -2) under photoelectric current (solid line; Dotted line represents dark current).(AM 1.5G, 100mW cm under simulated solar irradiation -2) photoelectric current surpass 4.2mA cm -2(bias voltage is 1.5V), corresponding solar energy converting Hydrogen Energy efficiency is 5.2%.

Claims (1)

1. the method for preparing lanthanium titanate oxynitride efficiency light electrode material, is characterized in that comprising the steps:
(1) utilize solid reaction process to prepare LaTiO 2the presoma La of N 2ti 2o 7, according to La 2ti 2o 7la and the molar weight proportioning of Ti take La 2o 3and TiO 2;
(2) raw material step (1) being taken, mixes and fully grinds; Be ground to the particle diameter that is distributed in 1 micron ~ 4 microns;
(3) in solid reaction process, the raw material mixing, at 800 ℃ ~ 1000 ℃ calcining 6h ~ 20h, is then cooled to room temperature, after grinding, at 1100 ℃ ~ 1400 ℃, calcines 6h ~ 20h again;
(4) the cooling rear grinding of product step (3) being obtained, obtains La 2ti 2o 7particle;
(5) La being prepared by step (4) 2ti 2o 7powder is at NH 3in atmosphere, 600 ℃ ~ 1000 ℃ thermal treatment 10h ~ 30h, obtain LaTiO 2n particle;
(6) LaTiO that utilizes electrophoretic deposition prepared by step (5) 2n particle deposition, in Conducting Glass, at air drying, can obtain LaTiO 2n membrana granulosa;
(7) LaTiO preparing in step (6) 2on N membrana granulosa, splash into TiCl 4methanol solution, then, by lower 300 ℃ of-700 ℃ of thermal treatments of its ammonia atmosphere 10 minutes ~ 60 minutes, has obtained the interconnective LaTiO of particle 2n optoelectronic pole;
(8) LaTiO preparing in step (7) 2n optoelectronic pole supports Co on surface 3o 4eelctro-catalyst, makes the LaTiO preparing 2n optoelectronic pole has high-efficiency solar converts hydrogen energy efficiency;
The electrophoretic deposition step of step (6); During electrophoresis, electrolytic solution adopts the acetone soln of iodine, by LaTiO 2n particulate material is suspended in this electrolytic solution; Anode and negative electrode all adopt conductive glass, and negative electrode is parallel with anode, and the conductive glass of negative electrode and anode 2/3 partly immerses the acetone soln of iodine, and the direct current that employing voltage is 10V ~ 40V is by the LaTiO suspending in electrolytic solution 2n particle deposition, at the conductive glass of negative electrode, obtains LaTiO 2n optoelectronic pole;
At LaTiO 2n optoelectronic pole supports Co on surface 3o 4eelctro-catalyst: NaOH solution is splashed into containing Co 2+the aqueous solution, form Co (OH) 2colloid, then by LaTiO 2n optoelectronic pole immerses this colloid, floods 10 minutes ~ 120 minutes; Take out again LaTiO 2n optoelectronic pole, water rinses LaTiO 2n optoelectronic pole, finally at 200 ℃ ~ 400 ℃ sintering 1h, by Co 3o 4be supported on LaTiO 2n optoelectronic pole surface.
CN201210499022.8A 2012-11-29 2012-11-29 Method for preparing LaTiO2N high-efficiency photoelectrode material Expired - Fee Related CN102995053B (en)

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CN105887130B (en) * 2016-04-12 2018-04-10 南京大学 A kind of method for electrically connecting agent and preparing photochemical catalyzing particle membrane electrode
CN107583661B (en) * 2016-07-08 2020-01-17 中国科学院大连化学物理研究所 Perovskite type lanthanum titanium oxynitride semiconductor photocatalyst and preparation and application thereof
CN106637287B (en) * 2016-10-17 2019-04-05 南京大学 A method of preparing tantalic acid lanthanum oxynitride efficiency light electrode
CN107308973B (en) * 2017-06-28 2020-05-22 西安交通大学 Basic cobalt phosphate nanoneedle composite LTON photocatalyst and preparation method and application thereof

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