CN104087966A - A preparing method of a photocatalytic electrode material for water-splitting hydrogen production - Google Patents

A preparing method of a photocatalytic electrode material for water-splitting hydrogen production Download PDF

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Publication number
CN104087966A
CN104087966A CN201410250276.5A CN201410250276A CN104087966A CN 104087966 A CN104087966 A CN 104087966A CN 201410250276 A CN201410250276 A CN 201410250276A CN 104087966 A CN104087966 A CN 104087966A
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titanium
agno
preparation
hydrogen production
solution
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田甜
倪培君
曹连忠
王凡
董海成
田小亭
孙远东
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INNER MONGOLIA RESEARCH INSTITUTE OF METAL MATERIAL
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INNER MONGOLIA RESEARCH INSTITUTE OF METAL MATERIAL
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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

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Abstract

A preparing method of a photocatalytic hydrogen production electrode material is disclosed. The method is characterized in that: titanium and an alloy thereof are adopted as the anode and an aqueous HF solution having a concentration of 0.2-0.7 wt% is adopted as an electrolyte; electrolytic oxidation is performed to prepare a titanium nano tube array; a silver nitrate solution is adopted as a dipping solution; and the titanium nano tube array is dipped in the silver nitrate solution, took out, washed, dried naturally, put into a muffle furnace, subjected to performing thermal processing and cooled inside the furnace to obtain the photocatalytic electrode material with excellent photocatalytic properties. The method is simple in process, low in cost, and high in photocatalytic efficiency.

Description

A kind of preparation method of photocatalytic hydrogen production by water decomposition electrode materials
Technical field
The present invention relates to a kind of preparation method that can utilize the photochemical catalyst electrode material of luminous energy hydrogen production by water decomposition, belong to photocatalyst material technical field, be specifically related to a kind of preparation method that can utilize visible ray water of decomposition to prepare the photochemical catalyst electrode material of hydrogen.
Background technology
The energy, as lifeblood and the power of development of world economy, is subject to the great attention of various countries, the whole world.Especially along with the huge consumption of Nonrenewable energy resources and the proposition of environmental friendliness energy concept, utilize the technology of sun power to become the problem that various countries scientist competitively studies.Utilizing luminous energy water of decomposition to prepare hydrogen is exactly a kind of method of effectively utilizing sun power wherein.Using water as raw material, utilize sun power to obtain efficient, the clean energy, to alleviating global energy dilemma, improve environment for human survival and there is very great economy and social effect.
Utilizing sun power key of hydrogen manufacturing from water is the exploitation of photochemical catalyst electrode material, can have as the material of photocatalyst a lot, comprising zinc oxide, stannic oxide, zirconium dioxide, Cadmium Sulfide, titanium oxide etc., but these materials only limit to ultraviolet region to the response frequency scope of light, cause energy conversion efficiency lower, can not utilize fully sun power to carry out photocatalysis hydrogen production.Therefore, development Stable Higher College, eco-friendly photocatalysis hydrogen production electrode materials become the emphasis of current research.
Japanese scientist Fujishima reported first in 1972 can in the photoelectrochemical cell of light anode, utilize UV-irradiation light anode dissolution water to prepare hydrogen and oxygen take titanium dioxide, established and utilized sun power to pass through the basis that semi-conductor catalytic decomposition water obtains clean Hydrogen Energy.Successful preparation along with the titanium oxide of this novel nano structure of titania nanotube array, this titanium oxide with bigger serface has been proved to be to be had photochemical catalyzing and prepares the ability of hydrogen [Wender H, Feil AF, Diaz LB, Riberio CS, Machado GJ, Migowski P, Weibel DE, Dupont J, Teixera SR (2011) ACS Appl Mater Interfaces 3:1359 – 1365; Meng Q, Wang J, Xie Q, Dong H, Li X (2011) Catal Today 165:145 – 149. Sun Y, Wang G, Yan K (2011) Int J Hydrogen Energy 36:15502 – 15508.], many scientists concentrate on how by titania nanotube array is carried out to modification, to improve its photocatalytic activity energy subsequently.An GM [J.Am. Chem.Soc., 131 (2009) 6648] adopts wet chemistry method to prepare the TiO that Pd quantum dot is modified 2nanotube dust nano material, has studied the application aspect photochemical catalysis.The TiO that Misra etc. [Langmuir, 24 (2008) 11276] obtain anodic oxidation 2nano-tube array is at PdCl 2in solution, soak for some time, thereby continue high-temperature calcination in hydrogen, obtain the TiO that Pd nano particle (10nm) is modified 2nano-tube array.[the Plasmonics such as Feng W, DOI 10.1007/s11468-012-9418-5] etc. utilize the method for Microwave Irradiation Assisted Chemical reaction to carry out silver to titania nanotube array to adulterate, improved the photocatalytic activity of titania nanotube array, the speed of catalyzing manufacturing of hydrogen has reached 1.34 μ mol/ (cm 2h).The research that utilizes precious metal to improve its photocatalysis performance as quantum dot modification titania nanotube array is also continuing, and method one side complex process, the cost reported are at present higher, and catalytic efficiency need further raising on the other hand.
Summary of the invention
The object of invention is to provide the preparation method of a kind of photocatalysis hydrogen production electrode materials that a kind of technique is simple, cost is lower, photocatalysis efficiency is higher.
The object of the invention is to realize in the following manner:
The invention is characterized in: using titanium and alloy thereof as anode, using the 0.2-0.7wt%HF aqueous solution as electrolytic solution, electrolytic oxidation is prepared titania nanotube array; Using Silver Nitrate as soak solution; Titania nanotube array is soaked in after silver nitrate solution, takes out and rinse, natural airing is placed on thermal treatment in retort furnace, obtains having the photochemical catalyst electrode material of excellent photocatalysis performance after furnace cooling.Specifically comprise the following steps:
A kind of preparation method of photocatalysis hydrogen production electrode materials
1) preparation of titania nanotube array: using titanium or titanium alloy substrate as anode, graphite flake or platinized platinum are as negative electrode, in the 0.2-0.7wt%HF aqueous solution, with the voltage anodic oxidation of 10-30V 20-40 minutes, take out, with distilled water, clean, normal temperature is dried, standby;
2) AgNO 3the preparation of soak solution: take Silver Nitrate and be dissolved in distilled water, preparation becomes 0.1-2 molL -1agNO 3obtain AgNO 3soak solution, is placed in darkroom standby;
3) will utilize titanium or the titanium alloy sheet of the titania nanotube array of preparation in step 1 to be placed in the AgNO of step 2 configuration 3soak solution 5-10 minute, takes out, with normal temperature dry for standby behind distilled water flushing surface;
4) thermal treatment: step 3 has been soaked to AgNO 3titanium after soak solution or titanium alloy sheet are placed in retort furnace, under air atmosphere, in 450-550 ℃ of degree, heat-treat, and furnace cooling after 60-240 minute, obtains a kind of photocatalysis hydrogen production electrode materials.
beneficial effect
A kind of photocatalysis hydrogen production electrode materials that adopts the inventive method to obtain has following features: electrode surface is loose porous, has larger specific surface area; the titanium oxide that electrode surface contains sharp state type and two kinds of crystalline structure of rutile-type, is conducive to improve the utilising efficiency of photon; electrode surface contains silver-colored quantum dot, is conducive to improve electrode photocatalytic activity. electrode surface total thickness is not more than 500nm, is combined closely with substrate titanium or titanium alloy, has photocatalysis performance steady in a long-term.
A kind of photocatalysis hydrogen production electrode materials of the present invention, carries out photocatalysis Decomposition hydrogen manufacturing to the potassium hydroxide solution of the 1mol/L that contains 5% methyl alcohol, and under 300 W xenon lamps irradiate, hydrogen manufacturing speed can reach 2-8 μ mol/ (cm 2h).
Accompanying drawing explanation
Fig. 1 is the material surface microtexture of embodiment 2,
The material surface X-ray diffractogram of Fig. 2 embodiment 2.
Embodiment
embodiment
Example 1:
Take pure titanium as matrix, and spectroscopically pure graphite sheet as anode, be take as negative electrode in surface after abrasive paper for metallograph polishing, cleaning, oven dry, take 0.5wt%HF solution as electrolytic solution, under 20V voltage, after anodic oxidation 20min, takes out, and soaks 0.1 molL after airing -1agNO 3solution 7 minutes, uses distilled water flushing sample surfaces, natural airing.Subsequently in retort furnace in 500 degree thermal treatment 1 hour, furnace cooling.The photochemical catalysis anode must with photocatalytic hydrogen production by water decomposition ability.
Example 2:
Take titanium alloy ti6al4v as matrix, and spectroscopically pure graphite sheet as anode, be take as negative electrode in surface after abrasive paper for metallograph polishing, cleaning, oven dry, take 0.3wt%HF solution as electrolytic solution, under 20V voltage, after anodic oxidation 40min, takes out, and soaks 0.5 molL after airing -1agNO 3solution 5 minutes, uses distilled water flushing sample surfaces, natural airing.Subsequently in retort furnace in 500 degree thermal treatment 3 hours, furnace cooling.The photochemical catalysis anode must with photocatalytic hydrogen production by water decomposition ability.
Example 3:
Take pure titanium as matrix, and platinized platinum as anode, be take as negative electrode in surface after abrasive paper for metallograph polishing, cleaning, oven dry, take 0.5wt%HF solution as electrolytic solution, under 20V voltage, after anodic oxidation 20min, takes out, and soaks 1 molL after airing -1agNO 3solution 5 minutes, uses distilled water flushing sample surfaces, natural airing.Subsequently in retort furnace in 450 degree thermal treatment 4 hours, furnace cooling.The photochemical catalysis anode must with photocatalytic hydrogen production by water decomposition ability.
Fig. 1 material surface microgram illustrates that this material surface is even, loose porous, has larger specific surface area.
Titanium Dioxide (Rutile) Top grade, sharp state type titanium oxide, silver-colored simple substance are contained in Fig. 2 illustrative material surface, and in figure, titanium peak is the diffraction peak of substrate titanium.

Claims (1)

1. a preparation method for photocatalysis hydrogen production electrode materials, is characterized in that:
1) preparation of titania nanotube array: using titanium or titanium alloy substrate as anode, graphite flake or platinized platinum are as negative electrode, in the 0.2-0.7wt%HF aqueous solution, with the voltage anodic oxidation of 10-30V 20-40 minutes, take out, with distilled water, clean, normal temperature is dried, standby;
2) AgNO 3the preparation of soak solution: take Silver Nitrate and be dissolved in distilled water, preparation becomes 0.1-2 molL -1agNO 3obtain AgNO 3soak solution, is placed in darkroom standby;
3) will utilize titanium or the titanium alloy sheet of the titania nanotube array of preparation in step 1 to be placed in the AgNO of step 2 configuration 3soak solution 5-10 minute, takes out, with normal temperature dry for standby behind distilled water flushing surface;
4) thermal treatment: step 3 has been soaked to AgNO 3titanium after soak solution or titanium alloy sheet are placed in retort furnace, under air atmosphere, in 450-550 ℃ of degree, heat-treat, and furnace cooling after 60-240 minute, obtains a kind of photocatalysis hydrogen production electrode materials.
CN201410250276.5A 2014-06-09 2014-06-09 A preparing method of a photocatalytic electrode material for water-splitting hydrogen production Pending CN104087966A (en)

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CN104492428A (en) * 2014-11-28 2015-04-08 东莞市青麦田数码科技有限公司 Silver or bismuth doped zirconium dioxide nanotube as well as preparation method and application thereof
CN108828329A (en) * 2018-04-27 2018-11-16 中国科学院地质与地球物理研究所 A kind of ocean electric field measurement sensor and preparation method thereof
CN111193037A (en) * 2019-10-22 2020-05-22 超威电源集团有限公司 Preparation method of aluminum-air battery cathode reduction catalyst
CN111215058A (en) * 2020-01-22 2020-06-02 中国石油大学(北京) Silver surface modified mixed crystal type titanium dioxide nano net photo-electro-catalytic composite material

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CN102525827A (en) * 2012-01-18 2012-07-04 重庆大学 Method for preparing medical titanium material with long-acting antibacterial property and good biocompatibility
CN103628112A (en) * 2013-11-20 2014-03-12 内蒙金属材料研究所 Preparation method of titanium-base titanium oxide-silver chloride composite coating material

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104492428A (en) * 2014-11-28 2015-04-08 东莞市青麦田数码科技有限公司 Silver or bismuth doped zirconium dioxide nanotube as well as preparation method and application thereof
CN104492428B (en) * 2014-11-28 2016-09-14 东莞市莞信企业管理咨询有限公司 A kind of Nano tube of zirconium dioxide of silver-doped or bismuth and its production and use
CN108828329A (en) * 2018-04-27 2018-11-16 中国科学院地质与地球物理研究所 A kind of ocean electric field measurement sensor and preparation method thereof
CN111193037A (en) * 2019-10-22 2020-05-22 超威电源集团有限公司 Preparation method of aluminum-air battery cathode reduction catalyst
CN111193037B (en) * 2019-10-22 2022-02-22 超威电源集团有限公司 Preparation method of aluminum-air battery cathode reduction catalyst
CN111215058A (en) * 2020-01-22 2020-06-02 中国石油大学(北京) Silver surface modified mixed crystal type titanium dioxide nano net photo-electro-catalytic composite material
CN111215058B (en) * 2020-01-22 2021-06-11 中国石油大学(北京) Silver surface modified mixed crystal type titanium dioxide nano net photo-electro-catalytic composite material

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