CN103599766A - Catalyst for photocatalytic water splitting hydrogen production and preparation method and application of catalyst - Google Patents
Catalyst for photocatalytic water splitting hydrogen production and preparation method and application of catalyst Download PDFInfo
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- CN103599766A CN103599766A CN201310598363.5A CN201310598363A CN103599766A CN 103599766 A CN103599766 A CN 103599766A CN 201310598363 A CN201310598363 A CN 201310598363A CN 103599766 A CN103599766 A CN 103599766A
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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 discloses a catalyst for photocatalytic water splitting hydrogen production. The catalyst consists of the following components in percent by mass: 95-99.9 percent of titanium dioxide and 0.1-0.5 percent of carbon. The catalyst is efficient, stable and environment-friendly, and the hydrogen production efficiency is over 100 micromole.g<-1>.h<-1>.
Description
Technical field
The invention belongs to a kind of catalyst and preparation method and application, be specifically related to a kind of modification TiO for preparing hydrogen for visible ray photodissociation water
2nanocrystalline catalyst and preparation method and application.
Background technology
The energy, as the lifeblood of World Economics and the power of social development, has been subject to the great attention of various countries.China's energy demand total amount is large and growth rate is fast, has become at present the second largest production of energy Guo He country of consumption that is only second in the world the U.S..Yet, account for its reserves of fossil fuel of world energy sources supply 90% day by day exhausted.And the use of fossil fuel has caused serious environmental pollution, the carbon dioxide (CO that combustion of fossil fuel discharges
2) be most important greenhouse gases.In nearly more than 100 years, the global earth's surface mean temperature 0.3-0.6 ℃ that risen, sea level rise 14-25cm.People have turned to sight clean, reproducible new forms of energy more and more.Hydrogen is gradually familiar with by people as a kind of clean, efficient and reproducible new forms of energy, will play remarkable effect, and will produce tremendous influence to global ecological environment in the sustainable development of global energy system.Hydrogen itself is nontoxic and renewable, only generates water while comparing hydrogen burning with other fuel, can not produce environmentally harmful polluters such as carbon monoxide, carbon dioxide, hydrocarbon, plumbous compound and dust granules, can realize real zero-emission.And the water that burning generates also can continue hydrogen manufacturing, iterative cycles use.Therefore, along with the arrival in " hydrogen economy " epoch, human society is urgently sought cost-effective, can realize the hydrogen producing technology of suitability for industrialized production.
Solar energy is the source of energy on the earth, is primary energy, is again regenerative resource.Its aboundresources, both can freely be used, again without transportation, to environment without any pollution.On the earth, seawater resources are abundant, take seawater as raw material, utilize solar energy to carry out photolysis of seawater and prepare hydrogen, by solar energy the hydrogen release in seawater out, after utilizing, generate again water, environment is not had any impact, the continuable method of environmental protection of can yet be regarded as.It is estimated that, as the hydrogen in seawater is all extracted, the total amount of heat that it produces is than also large 9000 times of all fossil fuel liberated heats on the earth.In addition, take seawater as raw material obtains in the process of the energy, can also slow down because greenhouse effects make global warming and cause the existence crisis that sea level rise, land surface reduces.Therefore, take seawater as prepared using solar energy obtains efficient, the clean energy-hydrogen, to alleviating global energy crisis, improve the mankind's living environment, there is very important and far-reaching economy and social effect.
Utilizing solar energy key of hydrogen manufacturing from seawater is the exploitation of catalyst, can be a lot of as the material of photochemical catalyst, comprise titanium dioxide (TiO
2), zinc oxide (ZnO), tin oxide (SnO
2), zirconium dioxide (ZrO
2), the many oxide sulfide semiconductor such as cadmium sulfide (CdS), but these materials are only effectively stable at ultraviolet region (wavelength is less than 400nm), and ultraviolet light only accounts for 4% left and right of sunshine gross energy, and a large amount of uses of ultraviolet light can destroy the ecological environment of the earth.Can be too low at the activated catalyst activity of visible region, and there is photoetch, need to suppress with sacrifice agent, cause energy conversion efficiency low, can not make full use of solar energy and carry out catalysis.Therefore, searching efficient stable, eco-friendly visible ray catalyst for preparing hydrogen become the important front edge direction of current research.
Summary of the invention
The object of this invention is to provide a kind of efficient stable, eco-friendlyly there is the modification TiO that photodissociation water that visible light catalysis activity is high is prepared hydrogen
2nanocrystalline catalyst and preparation method and application.
Catalyst quality percentage of the present invention consists of:
Titanium dioxide 95-99.9%, carbon 0.1-5%.
The preparation method of catalyst of the present invention is prepared in the steps below:
(1) by material with carbon element, according to mass ratio, be 1:(10-50 with the acid of 1-10 mol/L) ratio mix after 0.5-24 hour, add wherein titanium source, the mass ratio of titanium source and material with carbon element is 1-25:1, under stirring, react after 2-120 hour vacuum filtration, washing in 60-100 ℃ of dry 2-10 hour;
(2) by dried sample in air standing 5～120 minutes, proceed in inert gas in 400-1000 ℃ of roasting 2-10 hour, then under air atmosphere 450-600 ℃ of roasting 3-9 hour, obtain photochemical catalyst.
Material with carbon element as above can be CMK-1, active carbon or CMK-3.
Titanium as above source can be titanium tetraisopropylate, n-butyl titanium, tetrem amido titanium, four Propylamino titaniums or four butylamine base titaniums.
Inert gas as above can be nitrogen, argon gas or helium.
The application conditions of catalyst of the present invention is: in the ratio of catalyst and water, be 1 gram of catalyst: 100-500 ml water, and by catalyst and water mixing and stirring, logical after nitrogen 10-60 minute, under stirring, use luminous intensity for 100-250mW/cm
2, wavelength is 400-620nm irradiation reaction solution 2-8 hour.
Major advantage of the present invention is: the catalyst visible light activity the present invention relates to is high, and under the radiation of visible light of 400-620nm, hydrogen production efficiency is all at 100 μ molg
-1h
-1above.
The specific embodiment
Embodiment 1
5 grams of carbon molecular sieve CMK-1 are mixed with the sulfuric acid of 100 gram of 5 mol/L after 21 hours and filter, dry, add wherein 10 gram of four Propylamino titanium, under stirring, to react 120 hours, vacuum filtration, washing are also dried 6 hours in 80 ℃.To after in dried sample air standing 15 minutes, proceed in nitrogen in 500 ℃ of roastings 4 hours, then in the lower 450 ℃ of roastings of air atmosphere 9 hours, obtain photochemical catalyst, the consisting of of gained photochemical catalyst: titanium dioxide 95%, carbon 5%.By 1 gram of this catalyst and 200 ml water mix and blends, with the irradiation reaction solution of 400-620nm, luminous intensity is 100mW/cm
2, first logical nitrogen 20 minutes before illumination, illumination starts sample analysis after 5 hours and calculates the efficiency that produces hydrogen is 112 μ molg
-1h
-1.
Embodiment 2
5 grams of carbon molecular sieve CMK-3 are mixed with the nitric acid of 250 gram of 1 mol/L after 10 hours and add wherein 75 grams of n-butyl titaniums, react 2 hours under stirring, vacuum filtration, washing are also dried 2 hours in 100 ℃.To after in dried sample air standing 120 minutes, proceed in argon gas in 400 ℃ of roastings 10 hours, then in the lower 600 ℃ of roastings of air atmosphere 5 hours, obtain photochemical catalyst, the consisting of of gained photochemical catalyst: titanium dioxide 96.9%, carbon 3.1%.By 1 gram of this catalyst and 100 ml water mix and blends, with the irradiation reaction solution of 400-620nm, luminous intensity is 250mW/cm
2, logical nitrogen is 10 minutes before illumination, and illumination starts sample analysis after 2 hours and calculates the efficiency that produces hydrogen is 180 μ molg
-1h
-1.
Embodiment 3
The mixed in hydrochloric acid of 5 grams of active carbons and 75 gram of 10 mol/L is added to 5 grams of tetrem amido titaniums wherein after 5 hours, react 48 hours under stirring, vacuum filtration, washing are also dried 5 hours in 100 ℃.To after in dried sample air standing 5 minutes, proceed in helium in 1000 ℃ of roastings 5 hours, then in the lower 550 ℃ of roastings of air atmosphere 3 hours, obtain photochemical catalyst, the consisting of of gained photochemical catalyst: titanium dioxide 99.9%, carbon 0.1%.By 1 gram of this catalyst and 500 ml water mix and blends, with the irradiation reaction solution of 400-620nm, luminous intensity is 100mW/cm
2, first logical nitrogen 45 minutes before illumination, illumination starts sample analysis after 6 hours and calculates the efficiency that produces hydrogen is 105 μ molg
-1h
-1.
Embodiment 4
5 grams of carbon molecular sieve CMK-1 are mixed with the nitric acid of 50 gram of 2 mol/L after 0.5 hour and add wherein 56 grams of titanium tetraisopropylates, react 85 hours under stirring, vacuum filtration, washing are also dried 8 hours in 75 ℃.The oxidation of dried sample air is proceeded to after 90 minutes in argon gas in 600 ℃ of roastings 2 hours, then in the lower 500 ℃ of roastings of air atmosphere 5 hours, obtain photochemical catalyst, the consisting of of gained photochemical catalyst: titanium dioxide 99.1%, carbon 0.9%.By 1 gram of this catalyst and 300 ml water mix and blends, with the irradiation reaction solution of 400-620nm, luminous intensity is 150mW/cm
2, first logical nitrogen 30 minutes before illumination, illumination starts sample analysis after 8 hours and calculates the efficiency that produces hydrogen is 101.2 μ molg
-1h
-1.
Embodiment 5
The mixed in hydrochloric acid of 5 grams of carbon molecular sieve CMK-3 and 200 gram of 8 mol/L is added to 7.5 gram of four butylamine base titanium wherein after 24 hours, react 5 hours under stirring, vacuum filtration, washing are also dried 10 hours in 60 ℃.Dried sample air is proceeded to after standing 60 minutes in nitrogen in 800 ℃ of roastings 6 hours, then in the lower 500 ℃ of roastings of air atmosphere 6 hours, obtain photochemical catalyst, the consisting of of gained photochemical catalyst: titanium dioxide 95.8%, carbon 4.2%.By 1 gram of this catalyst and 200 ml water mix and blends, with the irradiation reaction solution of 400-620nm, luminous intensity is 200mW/cm
2, first logical nitrogen 60 minutes before illumination, illumination starts sample analysis after 4 hours and calculates the efficiency that produces hydrogen is 153 μ molg
-1h
-1.
Claims (6)
1. for a catalyst for photolysis water hydrogen, it is characterized in that catalyst quality percentage consists of:
Titanium dioxide 95-99.9%, carbon 0.1-5%.
2. the preparation method of a kind of catalyst for photolysis water hydrogen as claimed in claim 1, is characterized in that comprising the steps:
The ratio that is 1:10-50 according to mass ratio by the acid of material with carbon element and 1-10 mol/L was mixed after 0.5-24 hour, add wherein titanium source, the mass ratio of titanium source and material with carbon element is 1-25:1, reacts after 2-120 hour vacuum filtration, washing in 60-100 ℃ of dry 2-10 hour under stirring;
By dried sample in air standing 5～120 minutes, proceed in inert gas in 400-1000 ℃ of roasting 2-10 hour, then under air atmosphere 450-600 ℃ of roasting 3-9 hour, obtain photochemical catalyst.
3. the preparation method of a kind of catalyst for photolysis water hydrogen as claimed in claim 1, is characterized in that described material with carbon element is CMK-1, active carbon or CMK-3.
4. the preparation method of a kind of catalyst for photolysis water hydrogen as claimed in claim 1, is characterized in that described titanium source is titanium tetraisopropylate, n-butyl titanium, tetrem amido titanium, four Propylamino titaniums or four butylamine base titaniums.
5. the preparation method of a kind of catalyst for photolysis water hydrogen as claimed in claim 1, is characterized in that described inert gas is nitrogen, argon gas or helium.
6. the application of a kind of catalyst for photolysis water hydrogen as claimed in claim 1, it is characterized in that application conditions is: in the ratio of catalyst and water, be 1 gram of catalyst: 100-500 ml water, by catalyst and water mixing and stirring, logical after nitrogen 10-60 minute, under stirring, use luminous intensity for 100-250mW/cm
2, wavelength is 400-620nm irradiation reaction solution 2-8 hour.
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Citations (10)
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|---|---|---|---|---|
| US6017425A (en) * | 1995-09-18 | 2000-01-25 | Korea Research Institute Of Technology | Photocatalyst, preparation therefor and method for producing hydrogen using the same |
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| CN101670282A (en) * | 2009-10-19 | 2010-03-17 | 浙江博华环境技术工程有限公司 | Preparation method of load type nano titanium dioxide catalyst |
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| CN101829555A (en) * | 2010-05-26 | 2010-09-15 | 上海大学 | Method for preparing titanium dioxide/mesoporous carbon composite photocatalyst by electron beam irradiation |
-
2013
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| CN101053845A (en) * | 2006-04-10 | 2007-10-17 | 上海市七宝中学 | Sol-gel method preparing active carbon-titanium dioxide composite photocatalyst method and application of the said photocatalyst |
| CN100998934A (en) * | 2006-10-13 | 2007-07-18 | 中国石油大学(华东) | Loading type photocatalyst for treating phenol liguid phase pollutant and its preparation method and application |
| CN101244383A (en) * | 2008-03-13 | 2008-08-20 | 同济大学 | Process for producing absorbent charcoal loading titanium dioxide photocatalyst |
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Application publication date: 20140226 |