CN102489329B - Catalysis system for hydrogen generation by catalytic reduction of water with visible light, and preparation method thereof - Google Patents
Catalysis system for hydrogen generation by catalytic reduction of water with visible light, and preparation method thereof Download PDFInfo
- Publication number
- CN102489329B CN102489329B CN 201110366088 CN201110366088A CN102489329B CN 102489329 B CN102489329 B CN 102489329B CN 201110366088 CN201110366088 CN 201110366088 CN 201110366088 A CN201110366088 A CN 201110366088A CN 102489329 B CN102489329 B CN 102489329B
- Authority
- CN
- China
- Prior art keywords
- water
- cuo
- hydrogen generation
- visible light
- catalyzing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a catalysis system for hydrogen generation by catalytic reduction of water with visible light, and a preparation method thereof. The catalysis system comprises an eosin/rhodamine B (methyl red or vitamin 12) combined composite dye adopted as a sensitizing agent, carbon nanotubes adopted as a carrier and a light induced electron channel, and CuO adopted as an assistant catalyst. The preparation method comprises: stirring and mixing the carbon nanotubes and an aqueous solution of a copper salt; evaporating until no water exists to prepare a carbon nanotube-metal salt precursor; annealing the precursor in the air atmosphere to obtain CuO-loaded carbon nanotubes; placing the CuO-loaded carbon nanotubes into an aqueous solution containing a composite dye, and soaking under the protection of N2 to obtain the hydrogen generation catalysis system. According to the present invention, the catalysis system of the present invention provides high hydrogen generation activity for the hydrogen generation reaction by reduction of the water with the visible light in the presence of the sacrificial agent trolamine, can be used for the hydrogen generation by catalytic reduction of the water with the visible light, and provides a certain application values in the field of the hydrogen generation by reduction of the water with the sunlight.
Description
Technical field
The invention belongs to energy technology field, specifically, is for generating hydrogen by visible light photocatalytic reduction of water catalyst system and catalyzing and preparation method thereof about a kind of.
Background technology
The sunlight catalytic hydrogen producing technology is considered to very promising hydrogen production process, has obtained people's extensive concern.Carried out a large amount of research work this field people.At present, utilize the photocatalysis hydrogen production material of ultraviolet light substantially can satisfy the requirement of practical application.But, because 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 at visible region the focus that highly active hydrogen manufacturing material is the common concern of various countries scientific worker institute.In this respect, people adopt following several ways usually: 1) adulterate in wide band gap semiconducter; 2) build new valence band in the forbidden band; 3) preparation solid solution; 4) utilize the sensibilization of organic dyestuff, structure can efficiently utilize the photocatalysis system of visible light.
Result of study shows, method 4) be the preparation method of a up-and-coming efficient visible light producing hydrogen, catalyzing system, but the hydrogen production efficiency of dye sensitization photocatalysis system also needs further raising.The present inventor disclose in application number is 201110088792.9 Chinese invention patent application a kind of with the homogencous dyes eosin W or W S as sensitizer, CNT as carrier and light induced electron passage, the composite oxides catalyst that is used for generating hydrogen by visible light photocatalytic reduction of water as co-catalyst.Yet the load of composite oxides on CNT is very difficult, and the composite catalyst that how to obtain uniform component is also a difficult problem, has limited the selection of component in composite oxides.In addition, the present inventor also disclose in application number is 201110003168.4 Chinese invention patent application a kind of with the homogencous dyes eosin W or W S as sensitizer, CNT as the catalyst that be used for hydrogen manufacturing of the oxides such as carrier and light induced electron passage, cupric oxide as co-catalyst, but the hydrogen manufacturing effect is not satisfactory, wherein, a main cause is only to use a kind of dyestuff when building dye sensitization photocatalysis system.And the operating wavelength range of dyestuff is limited, can not cover full solar spectrum, and this makes the photocatalysis system can not utilize fully sunshine.And above-mentioned catalyst needs to use under strong alkaline condition, for extensive practicality, certain restriction is arranged.Therefore, need to improve existing catalyst system and catalyzing, expand it to the absorption region of sunshine, and can use under neutrallty condition.
Summary of the invention
Primary and foremost purpose of the present invention is to improve the shortcoming and defect of existing catalysis system, thereby a kind of catalyst system and catalyzing for generating hydrogen by visible light photocatalytic reduction of water is provided.
Another object of the present invention is to provide the preparation method of this catalyst system and catalyzing.
Another object of the present invention is to provide the application of this catalyst system and catalyzing.
The catalyst system and catalyzing of the catalyst system and catalyzing for generating hydrogen by visible light photocatalytic reduction of water of the present invention comprises sensitizer, carrier and light induced electron passage and co-catalyst, and wherein, described sensitizer is composite dye.
According to the present invention, composition and the percentage by weight of described composite dye are as follows:
Eosin W or W S 7.9～87.1%
Rhodamine B, methyl red or cobalamin 0.4～25%
According to the present invention, described carrier and light induced electron passage are CNT, and addition is 7.8～86.2%.
According to the present invention, described co-catalyst is CuO, and addition is 0.5～5.5%.
The preparation method of the catalyst system and catalyzing for generating hydrogen by visible light photocatalytic reduction of water of the present invention comprises the following steps:
(1) CNT, copper salt solution are mixed, will make Nano carbon tube-metal salt precursor body after the water evaporate to dryness;
(2) described presoma is calcined under air atmosphere obtained the CNT that load has CuO;
(3) load there is the CNT of CuO put into the aqueous solution that contains composite dye, at N
2Protection is lower soaks, and obtains described producing hydrogen, catalyzing system.
According to the present invention, described mantoquita is copper nitrate.
Catalyst system and catalyzing of the present invention can be used for generating hydrogen by visible light photocatalytic reduction of water.
The present invention has following beneficial effect:
1, the present invention uses composite dye as sensitizer, overcome the narrow problem of spectral absorption scope that exists when using homogencous dyes as sensitizer in the prior art, expand the absorption region of photocatalysis system to visible light, thereby improved photocatalysis hydrogen production efficient.
2, the present invention can use under neutrallty condition.
3, the present invention has higher hydrogen production activity for visible light reductive water hydrogen production reaction under the condition that the sacrifice agent triethanolamine exists, and can be used for the visible light photocatalytic reduction of water hydrogen making, has certain using value aspect the hydrogen manufacturing of sunshine reductive water.
Description of drawings
Fig. 1 is the XRD figure of CNT, and wherein (a) is CNT; (b) CNT of 6%CuO is arranged for load.
Fig. 2 is the TEM figure of load CNT that 6%CuO is arranged.
Fig. 3 is the UV-vis spectrogram of eosin, rhodamine B and eosin/rhodamine B solution.
Fig. 4 is the block diagram of the hydrogen output of the CuO-CNTs of different quality ratio and eosin-RhB.
Fig. 5 is the broken line graph of the hydrogen output of the CuO of different quality ratio and CNTs.
Fig. 6 is the broken line graph of the hydrogen output of the eosin of different quality ratio and RhB.
The specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described.Should be understood that following examples are only for explanation the present invention but not for limiting the scope of the invention.
In the context of the present invention, term " sacrifice agent " refers in photo catalytic reduction water hydrogen production process in order to guarantee that the catalysis recovery adds, mainly plays the reagent of reducing agent effect.Sacrifice agent used in the present invention comprises triethanolamine.
Embodiment1～10, the preparation of catalyst system and catalyzing
The catalyst system and catalyzing that is used for generating hydrogen by visible light photocatalytic reduction of water of the present embodiment, its composition and percentage by weight are as follows:
The preparation method of described catalyst system and catalyzing is as follows:
Press shown in table 1, with a certain proportion of CNT (CNTs, its X-ray diffraction (XRD) spectrogram is as shown in Fig. 1 (a)), 0.1molL
-1Copper nitrate aqueous solution join in beaker, dilute with water.After stirring 1h under 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, under air atmosphere, calcine 4h under 200 ℃～400 ℃, preferred 300 ℃, obtain CNT-CuO system, its XRD spectra is as shown in Fig. 1 (b), and transmission electron microscope (TEM) result is as shown in Figure 2.
A certain amount of CNT-CuO system is put in the solution that contains a certain proportion of eosin W or W S and rhodamine B (RhB)/methyl red (MR)/cobalamin (VB12), at N
2Lower 20min～the 24h that soaks of protection, preferred 30min obtains eosin-RhB/MR/VB12-CNT-CuO catalysis integration system.
Wherein, eosin, rhodamine B and eosin-rhodamine B solution spectrum figure as shown in Figure 3.
Actual conditions in preparation process is as shown in table 1:
Table 1, catalysis integration system and composition
Embodiment11, evaluating hydrogen production performance
Be that 15% triethanolamine solution is put into the photocatalysis hydrogen production evaluating apparatus with the 120mg eosin that obtains in embodiment 1～10-RhB/MR/VB12-CNT-CuO catalysis integration system and 60mL volume fraction, regulate pH to 7, lower logical high-purity N is stirred in the dark place
230min is with the O in the system of driving away
2
After gas collecting apparatus is full of water, opens light source and begin hydrogen manufacturing, reaction temperature is 45 ℃.Light source is the 1000W iodine-tungsten lamp, and the distance between light source and reactor is 15cm.Install optical filter between light source and reactor additional with the ultraviolet light of elimination wavelength less than 420nm.
After reaction 3h, close light source, use N
2With the H that produces in device for producing hydrogen
2Be purged in gas collecting apparatus.After purging fully, use gas chromatographic detection H
2Content.Gas-chromatography relevant parameter: post case temperature: 35 ℃; TCD detector temperature: 60 ℃; Injector temperature: 100 ℃; Electric current: 50mA; The knob number of turns: 4 circles.
Hydrogen manufacturing speed result is as shown in table 2:
Table 2, hydrogen manufacturing speed
Illustrate further that below various component in catalyst system and catalyzing and proportioning thereof are for the impact of hydrogen manufacturing effect.
As shown in Figure 4, the result of the hydrogen output of comparing embodiment 1～3 as can be known, when being 6% of CNTs quality at Cu0, the mass ratio of EosinY: RhB is that under the condition of 9.5: 0.5, the mass ratio of CuO-CNTs and composite dye is different has appreciable impact to hydrogen output.Hydrogen-producing speed is the highest when both mass ratioes are 1: 1, and mass ratio is that under the condition of 11: 1 or 1: 11, hydrogen-producing speed significantly descends, and illustrates that both mass ratioes are excessive or too smallly all be unfavorable for producing hydrogen.
As shown in Figure 5, the result of comparing embodiment 2,7,8 hydrogen output as can be known, when the mass ratio at CuO-CNTs and composite dye is 1: 1, the mass ratio of EosinY and RhB is under the condition of 9.5: 0.5, hydrogen-producing speed is along with the content of CuO-CNTs increases and increases, and when the content of CuO-CNTs greater than 6% the time, its hydrogen-producing speed tends to be steady.
As shown in Figure 6, when being 6% of CNTs quality at CuO, the mass ratio of CuO-CNTs and composite dye is under the condition of 1: 1, if only contain the eosin homogencous dyes in catalyst system and catalyzing, to use the 120mg catalyst, and the hydrogen output in 3h is 21.96 μ mol; And the catalyst system and catalyzing of RhB-CNT-CuO hydrogen output under equal conditions is 0.036 μ mol, produces hardly hydrogen.Simultaneously the result of comparing embodiment 2,4,5,6 hydrogen output as can be known, when the composite dye that uses eosin-RhB, be under the condition of 9.5: 0.5 at two kinds of constituent mass ratios, can reach maximum hydrogen output is 52.92 μ mol, be to use 2.41 times of homogencous dyes eosin, compare the more notable raising of homogencous dyes RhB of producing hardly hydrogen.
Simultaneously, use methyl red (MR) or cobalamin (VB12) also to obtain consistent result as composite dye.Under equal conditions, the result of comparing embodiment 9,10 hydrogen manufacturing speed as can be known, composite dye eosin-MR or eosin-VB12 improve respectively 1.92 and 2.8 times than the hydrogen manufacturing speed of homogencous dyes eosin.Above result shows utilizes composite dye can increase substantially utilization rate to light than homogencous dyes.
Claims (4)
1. catalyst system and catalyzing that is used for generating hydrogen by visible light photocatalytic reduction of water, comprise sensitizer, carrier and light induced electron passage and co-catalyst, it is characterized in that, described sensitizer is composite dye, formed by eosin W or W S and rhodamine B or methyl red or cobalamin, described carrier and photoproduction passage are CNT, and described co-catalyst is CuO, and composition and the percentage by weight of described catalyst system and catalyzing are as follows:
2. the preparation method of catalyst system and catalyzing claimed in claim 1 is characterized in that comprising the following steps:
(1) CNT, copper salt solution are mixed, will make Nano carbon tube-metal salt precursor body after the water evaporate to dryness;
(2) described presoma is calcined under air atmosphere obtained the CNT that load has CuO;
(3) load there is the CNT of CuO put into the aqueous solution that contains composite dye, at N
2Protection is lower soaks, and obtains described producing hydrogen, catalyzing system.
3. preparation method as claimed in claim 2, is characterized in that, described mantoquita is copper nitrate.
4. the application of catalyst system and catalyzing claimed in claim 1, is characterized in that, is used for generating hydrogen by visible light photocatalytic reduction of water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110366088 CN102489329B (en) | 2011-11-17 | 2011-11-17 | Catalysis system for hydrogen generation by catalytic reduction of water with visible light, and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110366088 CN102489329B (en) | 2011-11-17 | 2011-11-17 | Catalysis system for hydrogen generation by catalytic reduction of water with visible light, and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102489329A CN102489329A (en) | 2012-06-13 |
| CN102489329B true CN102489329B (en) | 2013-05-08 |
Family
ID=46181213
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110366088 Expired - Fee Related CN102489329B (en) | 2011-11-17 | 2011-11-17 | Catalysis system for hydrogen generation by catalytic reduction of water with visible light, and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102489329B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2568734C2 (en) * | 2013-10-23 | 2015-11-20 | Российская Федерация, от имени которой выступает Министерство промышленности и торговли Российской Федерации (Минпромторг России) | Device to produce and store atomic hydrogen |
| CN111204707B (en) * | 2020-01-14 | 2022-10-28 | 福建技术师范学院 | Application of perovskite material in dye-sensitized photolysis water-splitting hydrogen production |
| CN111229326B (en) * | 2020-03-09 | 2022-07-19 | 辽宁大学 | Preparation method and application of composite photocatalyst for hydrogen production by catalytic water photolysis |
| CN113769779B (en) * | 2021-08-16 | 2023-12-29 | 中化学朗正环保科技有限公司 | Photocatalyst for treating sewage containing amine organic matters, and preparation method and application thereof |
| CN113663708A (en) * | 2021-08-16 | 2021-11-19 | 中化学朗正环保科技有限公司 | High-efficiency photocatalytic material and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102039131B (en) * | 2011-01-07 | 2013-01-09 | 华东理工大学 | Catalyst for generating hydrogen by visible light photocatalytic reduction of water, and preparation method thereof |
-
2011
- 2011-11-17 CN CN 201110366088 patent/CN102489329B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102489329A (en) | 2012-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhao et al. | CeO2/3D g-C3N4 heterojunction deposited with Pt cocatalyst for enhanced photocatalytic CO2 reduction | |
| US20220042184A1 (en) | Preparation Method and Application of Non-noble Metal Single Atom Catalyst | |
| Tahir et al. | Selective photocatalytic reduction of CO2 by H2O/H2 to CH4 and CH3OH over Cu-promoted In2O3/TiO2 nanocatalyst | |
| Liu et al. | Charge transmission channel construction between a MOF and rGO by means of Co–Mo–S modification | |
| CN106732524A (en) | A kind of α/β bismuth oxide phase heterojunction photocatalyst and its preparation method and purposes | |
| CN102489329B (en) | Catalysis system for hydrogen generation by catalytic reduction of water with visible light, and preparation method thereof | |
| Chen et al. | Carbon nitride for photocatalytic water splitting to produce hydrogen and hydrogen peroxide | |
| CN107008467B (en) | Preparation method and application of heterojunction photocatalyst | |
| CN102039131B (en) | Catalyst for generating hydrogen by visible light photocatalytic reduction of water, and preparation method thereof | |
| Guo et al. | Enhancement of visible-light photocatalytic activity of Pt supported potassium niobate (Pt-KNbO3) by up-conversion luminescence agent (Er3+: Y3Al5O12) for hydrogen evolution from aqueous methanol solution | |
| CN106552651B (en) | Bi12O17Br2Synthesis and application method of photocatalyst | |
| CA2890789A1 (en) | Nanostructured metal oxide compositions for applied photocatalysis | |
| Zhang et al. | Facile synthesis of a ZnO–BiOI p–n nano-heterojunction with excellent visible-light photocatalytic activity | |
| Sarwar et al. | Synergistic effect of photo-reduced Ni–Ag loaded g-C3N4 nanosheets for efficient visible Light‐Driven photocatalytic hydrogen evolution | |
| Sun et al. | CdS quantum dots modified surface oxygen vacancy defect ZnO1-x-TiO2-x solid solution sphere as Z-Scheme heterojunctions for efficient visible light-driven photothermal-photocatalytic performance | |
| Zhang et al. | Bimetal Cu and Pd decorated Z-scheme NiGa2O4/BiVO4 photocatalyst for conversion of nitride and sulfide dyes to (NH4) 2SO4 | |
| CN102631919B (en) | Preparation method of copper-titanium-oxide mesomorphism material | |
| CN105905940A (en) | Preparation method of nickel titanate/titanium dioxide composite nanomaterial | |
| CN105148972A (en) | Preparation method and application of novel catalyst for reducing nitrate nitrogen in water under visible light condition | |
| CN109999878A (en) | For photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst and preparation method thereof | |
| CN107537520B (en) | Bismuth oxybromide-copper oxide nano composite photocatalyst and preparation method thereof | |
| Zhang et al. | Raspberry-like TiO 2 hollow spheres consisting of small nanocrystals towards efficient NO removal | |
| CN105771953A (en) | Preparation method of zinc titanate and titanium dioxide composite nano material | |
| Cui et al. | Heterojunction g-C3N4/CeO2/Bi2O3 composite for the photocatalytic purification of exhaust gas | |
| CN102218322B (en) | Catalyst for hydrogen production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130508 Termination date: 20131117 |