CN102039131B - Catalyst for generating hydrogen by visible light photocatalytic reduction of water, and preparation method thereof - Google Patents
Catalyst for generating hydrogen by visible light photocatalytic reduction of water, and preparation method thereof Download PDFInfo
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- CN102039131B CN102039131B CN2011100031684A CN201110003168A CN102039131B CN 102039131 B CN102039131 B CN 102039131B CN 2011100031684 A CN2011100031684 A CN 2011100031684A CN 201110003168 A CN201110003168 A CN 201110003168A CN 102039131 B CN102039131 B CN 102039131B
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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
The invention provides a catalyst for generating hydrogen by visible light photocatalytic reduction of water, and a preparation method thereof, wherein each 100mg of the catalysts contain 10-60mg of eosin-Y, 35-85mg of carbon nano tubes and 1-10mg of oxides. With the technical scheme of the invention, the eosin is used as a sensitizing agent, the carbon nano tubes are used as carriers and photogenerated electron channels, the oxides, such as copper oxide, are used as co-catalysts, so that hydrogen generation by visible light photocatalytic reduction of water is implemented. The catalyst has higher hydrogen generation activity under irradiation of the visible light, and can be used for generating hydrogen by visible light photocatalytic reduction of water. And the oxides substitute Pt to be used as the co-catalyst, thereby implementing non-platinum property of the catalyst.
Description
Technical field
The present invention relates to the solar hydrogen making field, particularly a kind of Catalysts and its preparation method for generating hydrogen by visible light photocatalytic reduction of water.
Background technology
At present, tellurian resource can't satisfy people's demand for a long time, and the use of fossil fuel has caused very large environmental pollution.The effective way that solar energy and Hydrogen Energy are considered to overcome the above problems.The unstability of solar energy supply is directly utilized it and is limited by very large.If can utilize solar hydrogen making, change solar energy into Hydrogen Energy, just can overcome the unstability of solar energy.Such solar energy-hydrogen energy system will be one of effective way that does not solve using energy source and ecological environment problem.
People mainly concentrate on direct heat decomposition method, thermochemical cycle, photocatalytic method and four aspects of Optical Electro-Chemistry decomposition method to the research of solar hydrogen making method.Wherein, photocatalytic method and the required device of Optical Electro-Chemistry decomposition method is simple, reaction condition is gentle is the Perfected process of hydrogen manufacturing.Cause scientific worker's broad interest, become forward position and the focus in solar hydrogen making field.At present, people have obtained to have very highly active hydrogen manufacturing material in the ultra-violet (UV) band.But the greater band gap of these materials does not absorb visible light.And the major part of solar spectrum drops on visible region, so the solar energy utilization ratio of these materials is very low.Therefore, obtain to have the focus that highly active hydrogen manufacturing material is the common concern of various countries scientific worker institute at visible region.Recently, people are subjected to the inspiration of DSSC research, and dye sensitization photocatalyst is inquired into.The result shows that this might become the new way that obtains the efficient visible light catalyst for preparing hydrogen.Selection face when Catalyst Design has been widened in the introducing of dye sensitizing agent greatly, significant for Future Development new type solar energy hydrogen manufacturing material, should obtain people's attention.That is that all right at present is ripe in the research of this respect, still has many problems to need to solve.In addition, in order to improve hydrogen production efficiency, people adopt the noble metals such as Pt to suppress the compound of photo-generated carrier usually.Because the Precious Metals Resources such as China Pt is very poor, the photochemical catalyst that this means the noble metals such as supporting Pt can not large-scale application in China, otherwise can cause hidden trouble to economic security, the national security of China.So the co-catalyst of the noble metals such as alternative Pt of seeking a kind of cheapness is very great for the practical application meaning of China's solar hydrogen making technology.In sum, designing and develop sensitizer, CNT and an oxide catalyst that is used for generating hydrogen by visible light photocatalytic reduction of water is of great significance for photo catalytic reduction water hydrogen manufacturing large-scale application tool in practice.
Summary of the invention
The purpose of this invention is to provide a kind of catalyst for generating hydrogen by visible light photocatalytic reduction of water, utilize cheap oxide to substitute the noble metals such as Pt of the prior art.
In order to solve the problems of the technologies described above, the present invention adopts following scheme:
A kind of catalyst for generating hydrogen by visible light photocatalytic reduction of water contains 10-60mg eosin W or W S, 35-85mg CNT and 1-10mg oxide in the described catalyst of every 100mg.
Described oxide is selected from cupric oxide, nickel oxide, ferrous oxide, di-iron trioxide, tri-iron tetroxide and chrome green.
Described oxide is cupric oxide.
The mass ratio of the eosin W or W S in the described catalyst, CNT and cupric oxide is 0.5: 1: 0.06.
Described oxide is iron oxide.
The mass ratio of the eosin W or W S in the described catalyst, CNT and iron oxide is 1.25: 1: 0.005.
A kind of method for preparing described catalyst for generating hydrogen by visible light photocatalytic reduction of water is characterized in that, at first prepares Nano carbon tube-metal salt precursor body; Described presoma is put into Muffle furnace, and under the air atmosphere, 200-400 ℃ of lower the calcining a few hours obtains the Nano carbon tube-metal oxide system; Described Nano carbon tube-metal oxide system is put into the aqueous solution N of eosin W or W S
2Protection is lower soaks, and separates, and obtains described catalyst.
By technique scheme of the present invention, utilize eosin as sensitizer, CNT is as carrier and light induced electron passage, and the oxides such as cupric oxide have been realized generating hydrogen by visible light photocatalytic reduction of water as co-catalyst.This catalyst has higher hydrogen production activity under radiation of visible light, can be used for the visible light photocatalytic reduction of water hydrogen making.And utilize oxide to replace Pt as co-catalyst, realized the non-platinum of catalyst.
Description of drawings
The standard x RD figure of Fig. 1 (a) CuO according to a preferred embodiment of the present invention, (b) XRD of multi-walled carbon nano-tubes figure, (c) XRD of multi-walled carbon nano-tubes-CuO system figure.
Fig. 2 is the TEM photo of multi-walled carbon nano-tubes-CuO (6%) system according to a preferred embodiment of the present invention.
Fig. 3 is the XPS spectrum of multi-walled carbon nano-tubes-CuO (6%) system according to a preferred embodiment of the present invention.
Fig. 4 is the FT-IR spectrum of according to a preferred embodiment of the present invention eosin W or W S, CNT and cupric oxide integration system (mass ratio is 0.5: 1: 0.06).
The specific embodiment
Below in conjunction with accompanying drawing, provide preferred embodiment of the present invention, and be described in detail, enable to understand better function of the present invention, characteristics.
The present invention utilizes eosin as sensitizer, and CNT is as carrier and light induced electron passage, and the oxides such as cupric oxide have been constructed catalyst as co-catalyst.Solve the problem that the hydrogen manufacturing of visible light reductive water and Pt co-catalyst substitute, obtained having the visible light catalytic system of higher hydrogen production efficiency.
Consisting of of catalyst according to the invention: every 100mg catalyst contains 10-60mg eosin W or W S, 35-85mg CNT, 1-10mg oxide co-catalyst.
According to a preferred embodiment of the present invention, described oxide co-catalyst is selected from cupric oxide, nickel oxide, ferrous oxide, di-iron trioxide, tri-iron tetroxide, chrome green.
Preparing the required medicine of catalyst of the present invention comprises: eosin W or W S: 5-100mg; CNT: 20-100mg; Slaine: 0.01-0.1mol, slaine refer to chloride, sulfate, nitrate, acetate of copper, nickel, cobalt, iron, chromium etc.
The preparation technology of catalyst according to the invention comprises: (I) aqueous solution with CNT, slaine joins in the beaker, then is diluted with water to predetermined.After the stirred for several hour, the water evaporate to dryness is obtained Nano carbon tube-metal salt precursor body under the room temperature.(II) presoma that obtains is put into Muffle furnace, under the air atmosphere, 200-400 ℃ of lower the calcining a few hours obtains the Nano carbon tube-metal oxide system.(III) aqueous solution N2 that this Nano carbon tube-metal oxide system is put into eosin W or W S protects the lower 20min-24h of immersion, separates, and obtains eosin W or W S, CNT and oxide catalyst.
Embodiment 1
With 80mg CNT, 0.6mL 0.1molL
-1Copper nitrate aqueous solution join in the 100mL beaker, be diluted with water to 20mL.After stirring 1h under the room temperature, the water evaporate to dryness is obtained Nano carbon tube-metal salt precursor body.
The presoma that obtains is put into Muffle furnace, and under the air atmosphere, 300 ℃ of lower calcining 3h obtain CNT-cupric oxide system.The standard X-ray diffraction XRD spectra of CuO is shown in Fig. 1 (a); The XRD collection of illustrative plates of multi-walled carbon nano-tubes is shown in Fig. 1 (b); The XRD collection of illustrative plates of CNT-cupric oxide system is shown in Fig. 1 (c).In addition, Fig. 2 shows the transmission electron microscope TEM photo of CNT-cupric oxide system; Fig. 3 shows the X-ray photoelectron spectroscopic analysis XPS spectrum of CNT-cupric oxide system.
60mg CNT-cupric oxide system is put in the solution of 60mL eosin W or W S (1mg/mL), at N
2Protection is lower soaks 30min, obtains eosin W or W S, CNT and copper oxide catalyst, and its FT-IR spectrum as shown in Figure 4.
Embodiment 2
With 85mg CNT, 0.4mL 0.1molL
-1Copper nitrate aqueous solution join in the 100mL beaker, be diluted with water to 20mL.After stirring 1h under the room temperature, the water evaporate to dryness is obtained Nano carbon tube-metal salt precursor body.(II) presoma that obtains is put into Muffle furnace, under the air atmosphere, 300 ℃ of lower calcining 3h obtain CNT-cupric oxide system.(III) above-mentioned CNT-cupric oxide system is put in the solution of 10mL eosin W or W S (1mg/mL), at N
2Protection is lower soaks 30min, obtains eosin W or W S, CNT and copper oxide catalyst.
Embodiment 3
With 35mg CNT, 0.4mL 0.1molL
-1Copper nitrate aqueous solution join in the 100mL beaker, be diluted with water to 20mL.After stirring 1h under the room temperature, the water evaporate to dryness is obtained Nano carbon tube-metal salt precursor body.(II) presoma that obtains is put into Muffle furnace, under the air atmosphere, 300 ℃ of lower calcining 3h obtain CNT-cupric oxide system.(III) above-mentioned CNT-cupric oxide system is put in the solution of 60mL eosin W or W S (1mg/mL), at N
2Protection is lower soaks 30min, obtains eosin W or W S, CNT and copper oxide catalyst.
Embodiment 4
(I) eosin W or W S, CNT and the copper oxide catalyst, the triethanolamine solution (2.5-20%V/V) that obtain among the embodiment 1 are put into the photocatalysis hydrogen production device.After pH value of solution is adjusted to 4-13, in the dark stir lower logical N
230min is with the O in the system of driving away
2
(II) gas collecting apparatus is full of water after, open light source, begin hydrogen manufacturing in the situation that optical filter exists.Reaction temperature is 20-70 ℃.
(III) behind the stoichiometric number hour, close light source, use N
2With the H in the device for producing hydrogen
2Be purged in the gas collecting apparatus.After purging fully, use gas chromatographic detection H
2Content.
The implementation step is as follows:
(a) be that 5% triethanolamine solution is put into homemade photocatalysis hydrogen production evaluating apparatus with 90mg eosin W or W S, CNT and cupric oxide integration system (mass ratio is 0.5: 1: 0.06) and 60mL volume fraction, regulate pH to 11, lower logical N is stirred in the dark place
230min is with the O in the system of driving away
2
(b) gas collecting apparatus is full of water after, open light source and begin hydrogen manufacturing, reaction temperature is 45 ℃.Light source is the halogen tungsten lamp of 1000W, and light source is 16cm apart from the distance of photocatalysis hydrogen production device.Install optical filter between light source and the reactor additional with the ultraviolet light of elimination wavelength less than 420nm.
(c) behind the reaction 3h, close light source, use N
2With the H that produces in the device for producing hydrogen
2Be purged in the gas collecting apparatus.After purging fully, with the content of gas chromatographic detection H2.The hydrogen manufacturing speed that obtains this catalyst can reach 1.18mmolh
-1G
-1Gas-chromatography relevant parameter: post case temperature: 35 ℃; TCD detector temperature: 60 ℃; Injector temperature: 100 ℃; Electric current: 50mA; The knob number of turns: 4 circles.
According to the liberation of hydrogen speed of the eosin W or W S that obtains in embodiments of the invention 2 or 3, CNT and copper oxide catalyst near 0.
The liberation of hydrogen speed of eosin W or W S according to a further advantageous embodiment of the invention, CNT and nickel oxide catalyst is 49.72 μ moleg
-1H
-1Eosin W or W S wherein: CNT: nickel oxide=1: 1: 0.07.
Liberation of hydrogen speed according to eosin W or W S, CNT and the ferric oxide catalyst of another preferred embodiment of the present invention is 2.524 μ moleg
-1H
-1Eosin W or W S wherein: CNT: iron oxide=1.25: 1: 0.005.
Above-described, be preferred embodiment of the present invention only, be not to limit scope of the present invention, the above embodiment of the present invention can also make a variety of changes.Be that simple, the equivalence that every claims according to the present patent application and description are done changes and modification, all fall into the claim protection domain of patent of the present invention.The present invention not detailed description be the routine techniques content.
Claims (5)
1. catalyst that is used for generating hydrogen by visible light photocatalytic reduction of water, it is characterized in that, contain 10-60mg eosin W or W S, 35-85mg in the described catalyst of every 100mg as CNT and the 1-10mg oxide of carrier and light induced electron passage, described oxide is selected from cupric oxide, nickel oxide, ferrous oxide, di-iron trioxide, tri-iron tetroxide and chrome green.
2. the catalyst for generating hydrogen by visible light photocatalytic reduction of water as claimed in claim 1 is characterized in that, described oxide is cupric oxide.
3. the catalyst for generating hydrogen by visible light photocatalytic reduction of water as claimed in claim 2 is characterized in that, the mass ratio of the eosin W or W S in the described catalyst, CNT and cupric oxide is 0.5:1:0.06.
4. the catalyst for generating hydrogen by visible light photocatalytic reduction of water as claimed in claim 1 is characterized in that, described oxide is iron oxide.
5. a method for preparing such as the described catalyst for generating hydrogen by visible light photocatalytic reduction of water of among the claim 1-4 each is characterized in that, at first prepares Nano carbon tube-metal salt precursor body; Described presoma is put into Muffle furnace, under the air atmosphere, calcine a few hours under the 200-400 ° of C, obtain the Nano carbon tube-metal oxide system; Described Nano carbon tube-metal oxide system is put into the aqueous solution N of eosin W or W S
2Protection is lower soaks, and separates, and obtains described catalyst.
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| CN103071530B (en) * | 2011-05-27 | 2014-11-12 | 中国科学院理化技术研究所 | Application of metal nanoparticles |
| CN102218544B (en) * | 2011-05-27 | 2013-05-01 | 中国科学院理化技术研究所 | Preparation method and application of metal nanoparticles |
| US20140295518A1 (en) * | 2011-09-30 | 2014-10-02 | Council Of Scientific & Industrial Research | Process for generation of hydrogen and syngas |
| CN102489329B (en) * | 2011-11-17 | 2013-05-08 | 华东理工大学 | Catalysis system for hydrogen generation by catalytic reduction of water with visible light, and preparation method thereof |
| CN102600901A (en) * | 2012-02-28 | 2012-07-25 | 华东理工大学 | Preparation method of catalyst for light-reducing water to produce hydrogen |
| CN103272598B (en) * | 2013-06-20 | 2015-07-01 | 南京信息工程大学 | Method for preparing straw-bundle-like copper oxide manometer photocatalyst |
| CN103480385B (en) * | 2013-09-13 | 2015-06-03 | 大连海事大学 | Supported catalyst preparing method and application of supported catalyst on electrode on dye-sensitized solar cell |
| CN104607208A (en) * | 2014-12-19 | 2015-05-13 | 华南理工大学 | A zinc cadmium sulfide/copper modified carbon nanotube composite, and a preparing method and applications thereof |
| TWI608991B (en) * | 2016-08-04 | 2017-12-21 | 陳昱煒 | Microwave-assisted method and apparatus for producing hydrogen |
| CN112871209B (en) * | 2021-02-18 | 2023-07-28 | 上海应用技术大学 | High-efficiency photocatalytic hydrogen production catalytic system and preparation method thereof |
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| CN1775348A (en) * | 2005-12-08 | 2006-05-24 | 华东理工大学 | Visible photocatalytic material |
| CN1974014A (en) * | 2006-12-14 | 2007-06-06 | 复旦大学 | Process of preparing nitrogen doped nanometer titania |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1775348A (en) * | 2005-12-08 | 2006-05-24 | 华东理工大学 | Visible photocatalytic material |
| CN1974014A (en) * | 2006-12-14 | 2007-06-06 | 复旦大学 | Process of preparing nitrogen doped nanometer titania |
Non-Patent Citations (1)
| Title |
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| 张晓杰等.染料敏化光催化还原水制氢.《分子催化》.2010,第24卷(第6期),第569-578页. * |
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