CN102091654B - Organic semiconductor visible light photocatalyst with membrane structure and preparation method and application thereof - Google Patents
Organic semiconductor visible light photocatalyst with membrane structure and preparation method and application thereof Download PDFInfo
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- CN102091654B CN102091654B CN2010105509081A CN201010550908A CN102091654B CN 102091654 B CN102091654 B CN 102091654B CN 2010105509081 A CN2010105509081 A CN 2010105509081A CN 201010550908 A CN201010550908 A CN 201010550908A CN 102091654 B CN102091654 B CN 102091654B
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- phenyl
- methyl butyrate
- perylene diimide
- diimide derivative
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 70
- 239000012528 membrane Substances 0.000 title claims abstract description 42
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims abstract description 114
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims abstract description 87
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims abstract description 87
- KJOLVZJFMDVPGB-UHFFFAOYSA-N perylenediimide Chemical class C=12C3=CC=C(C(NC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)NC(=O)C4=CC=C3C1=C42 KJOLVZJFMDVPGB-UHFFFAOYSA-N 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000001257 hydrogen Substances 0.000 claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 230000005684 electric field Effects 0.000 claims abstract description 6
- 238000007738 vacuum evaporation Methods 0.000 claims description 59
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 238000007740 vapor deposition Methods 0.000 claims description 32
- 239000011521 glass Substances 0.000 claims description 29
- 239000010453 quartz Substances 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 230000001105 regulatory effect Effects 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 238000007747 plating Methods 0.000 claims description 18
- 239000003792 electrolyte Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 230000005855 radiation Effects 0.000 claims description 8
- 229940075397 calomel Drugs 0.000 claims description 5
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 238000006392 deoxygenation reaction Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 241000549556 Nanos Species 0.000 abstract 3
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 74
- 239000003054 catalyst Substances 0.000 description 42
- 239000003795 chemical substances by application Substances 0.000 description 17
- 239000010410 layer Substances 0.000 description 17
- 238000012806 monitoring device Methods 0.000 description 15
- 238000002474 experimental method Methods 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 238000005286 illumination Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000003760 hair shine Effects 0.000 description 4
- 150000003949 imides Chemical class 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000003421 catalytic decomposition reaction Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- 244000188472 Ilex paraguariensis Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
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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 belongs to the field of producing hydrogen by carrying out photocatalysis decomposition on water with visible light and particularly relates to an organic semiconductor visible light photocatalyst with a membrane structure and a preparation method and application thereof. The visible light photocatalyst consists of the following three layers of membranes: a perylene diimide derivative membrane layer serving as a first layer; a membrane layer of a mixture of a perylene diimide derivative and [6, 6]-phenyl-C61 methyl butyrate, which serves as a second layer; and a [6, 6]-phenyl-C61 methyl butyrate membrane layer serving as a third layer, wherein the thickness of the perylene diimide derivative membrane layer is in the range of 10 to 30 nanos; the thickness of the membrane layer of the mixture of the perylene diimide derivative and the [6, 6]-phenyl-C61 methyl butyrate is in the range of 25 to 45 nanos; the molar ratio of the perylene diimide derivative to the [6, 6]-phenyl-C61 methyl butyrate is in the range of 4:1 to 11.6:1; and the thickness of the [6, 6]-phenyl-C61 methyl butyrate membrane layer is in the range of 3 to 15 nanos. The photocatalyst can be excited in a visible light region to decompose water into hydrogen and oxygen with the assistance from an electric field. The organic semiconductor visible light photocatalyst with the membrane structure can be used for producing hydrogen which is clean energy.
Description
Technical field
The invention belongs to visible light photocatalysis and decompose aquatic products hydrogen field; Be particularly related to the organic semiconductor visible-light photocatalyst and the method for making thereof of membrane structure, and utilize the organic semiconductor visible-light photocatalyst of this membrane structure to carry out the application of Optical Electro-Chemistry catalytic decomposition water generates clean energy resource hydrogen aspect.
Background technology
The conductor photocatalysis decomposition water be a kind of advanced person utilize a kind of method of conversion of solar energy for chemical energy, its mechanism of action is: under illumination, semiconductor is excited, and produces light induced electron and hole.Electronics and hole are diffused into semi-conductive surface then, and electronics is reduced into hydrogen to water, and the hole is oxidized to oxygen to water.The integral result of this variation is exactly that solar energy becomes chemical energy.Semiconductor species is various, and commonly used is exactly inorganic semiconductor now.1972, Fujishima and the Honda of Japan utilized that a kind of common inorganic semiconductor titanium dioxide is successful under the synergy of UV-irradiation and electric field to be hydrogen and oxygen to water decomposition.After this, various inorganic semiconductor catalyst are developed.Here have an important problem to need to solve: from practical angle, ultraviolet light only accounts for few part of sunshine, and therefore how developing visible light catalyst is exactly a difficult problem.In order to solve this difficult problem, software engineering researchers invent following several method:
1. seek the narrow semiconductor of band gap.The ferric oxide catalyst that the Gratzel exploitation of Sweden is more typically arranged.The ferric oxide source is simple, and is cheap, can absorb most of visible light, and very stable.Make membranaceous electrode to ferric oxide, under visible light radiation, its electricity conversion can reach more than 60%.
2. the semiconductor doping metal or the nonmetalloid of greater band gap.This is a most popular method of utilizing the inorganic semiconductor of some very good greater band gap.More typical example is exactly that the people such as Asahi of Japan in 2002 have developed the titanium dioxide that a kind of nitrogen mixes, and is published in (R.Asahi, T.Morikawa on " science " magazine of the U.S.; T.Ohwaki, K.Aoki, Y.Taga; Science, 2002,293; 269-271), this catalyst has more intense visible absorption, is a kind of reasonable visible light catalyst.Also have the Khan etc. of Japan to develop the titanium dioxide that a kind of carbon is modified, also be published on " science " magazine of the U.S. (Shahed U.M.Khan, Mofareh Al-Shahry, William B.Ingler Jr., Science, 2002,2243-2245).The band gap of the titanium dioxide of preparation has dropped to 2.32eV from 3.00eV in this way, and it can absorb most visible lights, thereby makes catalytic efficiency greatly increase, and the efficient of photoelectrocatalysis decomposition water has reached 8.35%.
Though above-mentioned two kinds of methods can solve inorganic semiconductor visible absorption problem, yet these two kinds of methods also have the defective of self.In other words; The inorganic semiconductor that the band gap that searches out now is narrower; It is exactly not cause researcher's extensive sympathetic response because conduction band is too low that most of energy level can not mate (conduction band is too low to be difficult to reduce water, or valence band is too high-leveled and difficult with the water oxidation) ferric oxide catalyst for example above-mentioned.On the other hand, be the method for a reasonable solution visible absorption though mix, yet with regard to titanium dioxide, element nearly all in the periodic table of elements all tried, and did not still obtain better catalyst, must make us disappointed to these methods.
At a few visible absorption can be arranged, simultaneously in the inorganic semiconductor of the decomposition water entirely that matees again of energy level, more typically be exactly the Zou Zhi of Nanjing University just grade in a job that Japan did; Be published in (Zhigang Zou, Jinhua Ye, Kazuhiro Sayama&HironoriArakawa on " nature " magazine of Britain; Nature; 2001,414,625-627).This catalyst chemical structure is In
1-xNi
xTaO
4(x=0-0.2), have reasonable full decomposition water performance, yet quantum efficiency is lower, is merely 0.66%).The Domen of Japan etc. developed the solid solution catalyst of a kind of gallium nitride and zinc oxide in 2006, also had reasonable full decomposition water performance, 420nm～440nm between visible region, and quantum yield has reached 2.5%.Though later on much being operated in this respect has certain breakthrough in addition, yet all fail to increase considerably quantum yield.
Since doctor Deng Qingyun of Kodak in 1987 found that organic semiconductor is luminous, the various application studies of organic semi-conductor had been made significant headway.Organic semiconductor has the unexistent advantage of a lot of inorganic semiconductors, such as handling ease, regulates molecular structure easily and causes visible absorption, and the conduction band valence band also can be regulated through molecular structure, and kind is a lot.In a word, the above-mentioned inorganic semiconductor organic semiconductor that is difficult to accomplish can solve easily.The present application of organic semiconductor includes OLED, field-effect transistor and solar cell.What deserves to be mentioned is the application of organic semiconductor on solar cell.Be used in still doctor Deng Qingyun on the solar cell to organic semiconductor at first, yet efficient is very low, is about 0.1%.Your professor of the black square of the U.S. utilized the p-n hetero-junctions to increase substantially the efficient of organic semiconductor solar cell afterwards, was about 1.5～2%, came compared with first, had improved tens times.After this professor Forrest of Princeton university has developed another kind of membranaceous smooth anode material with sandwich construction, is published in (Peter Peumans, Soichi Uchida and Stephen R.Forrest on " nature " magazine of Britain; Nature; 2003,425,158-162); This structure has improved the efficient of separation of charge greatly, makes energy conversion efficiency reach 3.5%.The Jin Young Kim of the U.S. in 2007 utilizes a kind of film plating process very easily to make the light anode of a multi-layer film structure, and related work is published in (J.Young Kim, Kwanghee Lee on " science " magazine of the U.S.; Nelson E.Coates, Daniel Moses, Thuc-QuyenNguyen; Mark Dante, Alan J.Heeger, Science; 2007,222-225).This organic multilayer film is made with whirler; Manufacturing process is very simple; Earlier needing the organic semiconductor of plated film to be dissolved in the organic solvent; Form solution, drip to this solution on the electro-conductive glass of high speed rotating on the spin-coating appearance then, thickness can be controlled by rotating speed and solution concentration.The film of making in this way, not only method is simple, and has very high electricity conversion, up to 6%.
Although organic semi-conductor is used a lot, yet, also be not applied to this outstanding material above the photoelectrocatalysis decomposition water so far.On the other hand; Also have a vital problem still not solve about the photoelectrocatalysis decomposition water; How to solve the limitation of inorganic semiconductor on the photoelectrocatalysis decomposition water; Promptly how to seek and a large amount of can absorb visible light, can on energy level, mate again, but also have catalyst than advantages of higher stability.Various other application of organic semiconductor show that its lot of superiority might be embodied in above the photoelectrocatalysis decomposition water, that is to say to utilize organic semi-conductor adjustability of structure and the limitation that remedies above-mentioned inorganic semiconductor of a great variety.
Summary of the invention
One of the object of the invention provides a kind of organic semiconductor visible-light photocatalyst of membrane structure.
Two of the object of the invention provides a kind of preparation method of organic semiconductor visible-light photocatalyst of membrane structure.
Three of the object of the invention provides the application that the organic semiconductor visible-light photocatalyst that utilizes membrane structure carries out Optical Electro-Chemistry catalytic decomposition water generates clean energy resource hydrogen aspect.
The present invention utilizes organic semiconductor to absorb visible light; Water can be resolved into the function of hydrogen and oxygen then; Thereby the organic semiconductor visible-light photocatalyst of membrane structure of the present invention is widely used in photoelectrocatalysis decomposition water aspect, produces clean energy resource hydrogen with cheapness.
Core of the present invention not only provides a kind of organic semiconductor visible-light photocatalyst of membrane structure; But also the organic semiconductor that utilizes this membrane structure visible-light photocatalyst is provided; Can effectively resolve into water the function of hydrogen and oxygen; To solve existing energy problem, realize the using value of this film.
The organic semiconductor visible-light photocatalyst of membrane structure of the present invention is made up of three layers of organic layer; Middle mixed layer has play a part crucial on separation of charge; Because under radiation of visible light, organic semiconductor forms electron hole pair, but this electron hole pair is difficult to separate into electronics and hole freely; And the existence of mixed layer makes electronics and hole separative efficiency greatly increase; Electronics and hole are diffused into semi-conductive surface then, and electronics is reduced into hydrogen to water, and the hole is oxidized to oxygen to water.Obviously; This multi-layer film structure catalyst has following characteristics: (1) catalyst is made up of two kinds of common organic molecules; Can reduce cost on the one hand, two kinds of molecule differing absorption spectrum can absorb wider visible light on the other hand, thereby improve the utilization rate of visible light.(2) very important basic reaction that the photoelectrocatalysis decomposition water is such has expanded in the organic semiconductor system that is more prone to seek and regulates and control; Can synthesize the organic semiconductor of various needs through the chemical constitution of regulating organic molecule, increase the possibility of seeking better catalyst greatly; (3) utilize have sandwich construction film as photochemical catalyst; The existence of middle mixed layer has solved organic semiconductor separation of charge problem of difficult; Make the density of free charge increase greatly, the surface that is diffused into electrode through the free electron hole then strengthens the efficient of photoelectrocatalysis decomposition water.
The organic semiconductor visible-light photocatalyst that can be under the exciting of visible light resolves into the membrane structure of hydrogen and oxygen to water of the present invention is made up of ground floor trilamellar membrane: have machine partly to lead body perylene diimide derivative rete (thickness is preferably 10～30 nanometers); The second layer: You machine Ban Dao Ti perylene diimide derivative and organic semiconductor [6,6]-phenyl-C
61The mixture film that methyl butyrate is combined closely, wherein ， perylene diimide derivative and [6,6]-phenyl-C
61The mol ratio of methyl butyrate is 4: 1～11.6: 1 (thickness is preferably 25～45 nanometers); The 3rd layer: organic semiconductor [6,6]-phenyl-C
61Methyl butyrate rete (thickness is preferably 3～15 nanometers).
Suo Shu De perylene diimide derivative Bao Kuo perylenetetracarboxylic dianhydride is with there is aliphatic hydrocarbon substituting group (below 20 carbon atoms) on the perylene diimide N atom; Suo Shu De perylene diimide derivant structure is:
Wherein: R, R ' are C independently
20Following aliphatic hydrocarbon substituting group.
Described [6,6]-phenyl-C
61The structure of methyl butyrate is:
Wherein Me is a methyl.
The preparation method of the organic semiconductor visible-light photocatalyst of membrane structure of the present invention may further comprise the steps:
(1). will adorn perylene diimide derivative and [6,6]-phenyl-C respectively
61Two quartz containers of methyl butyrate are placed in two crucibles of same vacuum evaporation appearance, above vacuum evaporation appearance cavity, put electro-conductive glass ITO, are evacuated to 1 * 10 then
-5～4 * 10
-5Pa;
(2). to add the electric current that hot charging carries the crucible of perylene diimide derivative be 1.5～1.8A in control on the vacuum evaporation appearance of regulating step (1); add hot perylene diimide derivative; make perylene diimide derivative vapor deposition on electro-conductive glass ITO, must arrive perylene diimide derivative rete; Film thickness monitoring device on the close observation vacuum evaporation appearance stops plated film when the thickness of perylene diimide derivative rete preferably arrives 10～30 nanometers simultaneously;
(3). need not to take out; Then and then on the vacuum evaporation appearance of regulating step (2) control to add the electric current that hot charging carries the crucible of perylene diimide derivative be that 1.5～1.8A steams plating perylene diimide derivative; Regulate simultaneously to control on the vacuum evaporation appearance to heat and be mounted with [6,6]-phenyl-C
61The electric current of the crucible of methyl butyrate is 1.3～1.6A vapor deposition [6,6]-phenyl-C
61Methyl butyrate ， Shi perylene diimide derivative and [6,6]-phenyl-C
61Methyl butyrate vapor deposition simultaneously must arrive perylene diimide derivative and [6,6]-phenyl-C on perylene diimide derivative rete on the perylene diimide derivative rete of step (2) gained
61The mixture film that methyl butyrate is combined closely; Film thickness monitoring device on the while close observation vacuum evaporation appearance is as the Du De of institute perylene diimide derivative and [6,6]-phenyl-C
61The thickness of the mixture film that methyl butyrate is combined closely stops plated film when preferably arriving 25～45 nanometers, wherein ， perylene diimide derivative and [6,6]-phenyl-C
61The mol ratio of methyl butyrate is 4: 1～11.6: 1;
(4). need not to take out, then and then on the vacuum evaporation appearance of regulating step (3) the control heating be mounted with [6,6]-phenyl-C
61The electric current of the crucible of methyl butyrate is 1.3～1.6A vapor deposition [6,6]-phenyl-C
61Methyl butyrate makes [6,6]-phenyl-C
61The methyl butyrate vapor deposition is at step (3) gained De perylene diimide derivative and [6,6]-phenyl-C
61， Zai perylene diimide derivative and [6,6]-phenyl-C on the mixture film that methyl butyrate is combined closely
61Obtain [6,6]-phenyl-C on the mixture film that methyl butyrate is combined closely
61The methyl butyrate rete; Film thickness monitoring device on the while close observation vacuum evaporation appearance is as gained [6,6]-phenyl-C
61The thickness of methyl butyrate rete stops plated film when preferably arriving 3～15 nanometers; At this moment just accomplish whole process of plating, obtain the organic semiconductor visible-light photocatalyst of described membrane structure.
The organic semiconductor visible-light photocatalyst of membrane structure of the present invention is used for splitting water into hydrogen and oxygen exciting under the synergy with electric field of visible light.
Described being used in the method that splits water into hydrogen and oxygen under the synergy with electric field that excites of visible light is:
(1). one can be airtight the quartz reaction container in add 15～55mM KNO
3As electrolyte, use 1M H
2SO
4Above-mentioned electrolytical pH value furnishing 1～3.As required, can in above-mentioned electrolyte, add or not add various sacrifice agents.
(2). behind the quartz reaction container of airtight step (1) with inert gas (like argon gas) deoxygenation; And in this quartz reaction container, make up a photoelectrocatalysis battery three-electrode system; Wherein: working electrode is: the organic semiconductor visible-light photocatalyst light anode of membrane structure; Reference electrode is: calomel electrode to electrode is: platinum electrode; (irradiation of λ＞420nm) down, the connection electrochemical workstation carries out the photoelectrocatalysis decomposition water at visible light; The gas that is produced is used gas chromatographic detection.
Illumination experiment condition a: halogen lamp is placed in the double glazing condensation sleeve pipe, on every side around recirculated cooling water.(λ＞420nm) places the chuck outside to excise the light below the 420nm fully and guarantee that reaction only carries out under visible light for cut-off type optical filter.
Two organic molecular species in the organic semiconductor visible-light photocatalyst of membrane structure of the present invention are to become three layers according to certain ratio with the order vapor deposition; This catalyst can effectively utilize visible light, under the assistance of bias voltage, can effectively resolve into hydrogen and oxygen to water.
The present invention has made up a kind of organic semiconductor visible-light photocatalyst with membrane structure of height practicality; Under radiation of visible light, produce electronics and hole; Respectively water reduction be oxidized to hydrogen and oxygen; No matter the system of a kind of simple photoelectrocatalysis decomposition water is so still developed organic semi-conductor new application all have great scientific meaning to the cheap clean energy resource hydrogen of producing in the industry.
Below in conjunction with accompanying drawing and embodiment the present invention is done further detailed explanation.
Description of drawings
Fig. 1. the organic semiconductor film catalyst of the embodiment of the invention 1 is at photoelectrocatalysis battery three-electrode system (working electrode: organic semiconductor film catalyst light anode; Reference electrode: calomel electrode; To electrode: platinum electrode), visible light (under the irradiation of λ＞420nm), the design sketch of the photoelectrocatalysis decomposition water of different organic semiconductor film catalysts.
Fig. 2. the organic semiconductor visible-light photocatalyst of the membrane structure of the embodiment of the invention 4 is in three-electrode system, and (irradiation of λ＞420nm) is the design sketch of decomposition water generation hydrogen and oxygen down at visible light.
Fig. 3. the organic semiconductor visible-light photocatalyst of the membrane structure of the embodiment of the invention 5 in three-electrode system, with different sacrifice agents as hole trapping agents, at visible light (the catalytic activity design sketch under the irradiation of λ＞420nm).
Fig. 4. the organic semiconductor visible-light photocatalyst of the membrane structure of the embodiment of the invention 7 in three-electrode system, with KI (5mM) as sacrifice agent, at visible light (the catalytic stability design sketch under the irradiation of λ＞420nm).
Fig. 5. the organic semiconductor visible-light photocatalyst of the membrane structure of the embodiment of the invention 8 is in three-electrode system, at visible light (the electricity conversion design sketch under the irradiation of λ＞420nm).
The specific embodiment
Perylenetetracarboxylic dianhydride [6,6]-phenyl-C
61Methyl butyrate, Me are methyl
Utilize Shu perylenetetracarboxylic dianhydride and [6,6]-phenyl-C
61Methyl butyrate makes five kinds of different films of film a～d, and concrete grammar is following:
The preparation of film a:
(1) quartz container with Zhuan You perylenetetracarboxylic dianhydride is placed in the crucible of a vacuum evaporation appearance, above vacuum evaporation appearance cavity, puts the electro-conductive glass ITO of 4 * 2cm, is evacuated to 1 * 10 then
-5～4 * 10
-5Pa;
(2). to add the electric current that hot charging carries perylenetetracarboxylic dianhydride's crucible be 1.5～1.8A in control on the vacuum evaporation appearance of regulating step (1); add hot perylenetetracarboxylic dianhydride; make perylenetetracarboxylic dianhydride's vapor deposition on electro-conductive glass ITO, one layer of perylenetetracarboxylic dianhydride's rete of plating on electro-conductive glass ITO; Film thickness monitoring device ， on the close observation vacuum evaporation appearance stops plated film when the thickness of perylenetetracarboxylic dianhydride's rete arrives 48 nanometers simultaneously, obtains film a.
The preparation of film b:
(1) [6,6]-phenyl-C will be housed
61A quartz container of methyl butyrate is placed in the crucible of a vacuum evaporation appearance, above vacuum evaporation appearance cavity, puts the electro-conductive glass ITO of 4 * 2cm, is evacuated to 1 * 10 then
-5～4 * 10
-5Pa;
(2). the control heating is mounted with [6,6]-phenyl-C on the vacuum evaporation appearance of regulating step (1)
61The electric current of the crucible of methyl butyrate is 1.3～1.6A, heating [6,6]-phenyl-C
61Methyl butyrate makes [6,6]-phenyl-C
61The methyl butyrate vapor deposition plates one deck [6,6]-phenyl-C on electro-conductive glass ITO on electro-conductive glass ITO
61The methyl butyrate rete; Film thickness monitoring device on the while close observation vacuum evaporation appearance is as [6,6]-phenyl-C
61The thickness of methyl butyrate rete stops plated film when arriving 48 nanometers, obtains film b.
The preparation of film c:
(1) will distinguish Zhuan You perylenetetracarboxylic dianhydride and [6,6]-phenyl-C
61Two quartz containers of methyl butyrate are placed in two crucibles of same vacuum evaporation appearance, above vacuum evaporation appearance cavity, put the electro-conductive glass ITO of 4 * 2cm, are evacuated to 1 * 10 then
-5～4 * 10
-5Pa;
(2). to add the electric current that hot charging carries perylenetetracarboxylic dianhydride's crucible be that 1.5～1.8A steams the plating perylenetetracarboxylic dianhydride in control on the vacuum evaporation appearance of regulating step (1), regulates simultaneously that the control heating being mounted with [6,6]-phenyl-C on the vacuum evaporation appearance
61The electric current of the crucible of methyl butyrate is 1.3～1.6A vapor deposition [6,6]-phenyl-C
61Methyl butyrate ， Shi perylenetetracarboxylic dianhydride and [6,6]-phenyl-C
61Vapor deposition is on the electro-conductive glass ITO of step (1) simultaneously for methyl butyrate, and De is Dao perylenetetracarboxylic dianhydride and [6,6]-phenyl-C on electro-conductive glass ITO
61The mixture film that methyl butyrate is combined closely; Film thickness monitoring device on the while close observation vacuum evaporation appearance is as the Du De perylenetetracarboxylic dianhydride of institute and [6,6]-phenyl-C
61The thickness of the mixture film that methyl butyrate is combined closely stops plated film when arriving 58 nanometers! Zhe Shi perylenetetracarboxylic dianhydride and [6,6]-phenyl-C
61The mol ratio of methyl butyrate is 11.6: 1), obtain film c.
The preparation of film d:
(1) will distinguish Zhuan You perylenetetracarboxylic dianhydride and [6,6]-phenyl-C
61Two quartz containers of methyl butyrate are placed in two crucibles of same vacuum evaporation appearance, above vacuum evaporation appearance cavity, put the electro-conductive glass ITO of 4 * 2cm, are evacuated to 1 * 10 then
-5～4 * 10
-5Pa;
(2). to add the electric current that hot charging carries perylenetetracarboxylic dianhydride's crucible be that 1.5～1.8A steams the plating perylenetetracarboxylic dianhydride in control on the vacuum evaporation appearance of regulating step (1), on electro-conductive glass ITO, plates perylenetetracarboxylic dianhydride's layer of one deck 20 nanometer thickness earlier, stops plated film; Regulate then to control on the vacuum evaporation appearance to heat and be mounted with [6,6]-phenyl-C
61The electric current of the crucible of methyl butyrate is 1.3～1.6A vapor deposition [6,6]-phenyl-C
61Methyl butyrate, on perylenetetracarboxylic dianhydride's rete, plating a layer thickness is [6, the 6]-phenyl-C of 29 nanometers
61Methyl butyrate rete ， perylenetetracarboxylic dianhydride and [6,6]-phenyl-C
61The gross thickness of methyl butyrate composite film is 49 nanometers, obtains film d.
The preparation of film e:
(1) will distinguish Zhuan You perylenetetracarboxylic dianhydride and [6,6]-phenyl-C
61Two quartz containers of methyl butyrate are placed in two crucibles of same vacuum evaporation appearance, above vacuum evaporation appearance cavity, put the electro-conductive glass ITO of 4 * 2cm, are evacuated to 1 * 10 then
-5～4 * 10
-5Pa;
(2). to add the electric current that hot charging carries perylenetetracarboxylic dianhydride's crucible be 1.8A in control on the vacuum evaporation appearance of regulating step (1); add hot perylenetetracarboxylic dianhydride; make perylenetetracarboxylic dianhydride's vapor deposition on electro-conductive glass ITO, one layer of perylenetetracarboxylic dianhydride's rete of plating on electro-conductive glass ITO; Film thickness monitoring device ， on the close observation vacuum evaporation appearance stops plated film when the thickness of perylenetetracarboxylic dianhydride's rete arrives 20 nanometers simultaneously;
(3). need not to take out, then and then on the vacuum evaporation appearance of regulating step (2) control to add the electric current that hot charging carries perylenetetracarboxylic dianhydride's crucible be that 1.8A steams the plating perylenetetracarboxylic dianhydride, regulate simultaneously that the control heating being mounted with [6,6]-phenyl-C on the vacuum evaporation appearance
61The electric current of the crucible of methyl butyrate is 1.3A vapor deposition [6,6]-phenyl-C
61Methyl butyrate ， Shi perylenetetracarboxylic dianhydride and [6,6]-phenyl-C
61Methyl butyrate simultaneously vapor deposition on ， Zai perylenetetracarboxylic dianhydride rete on step (2) the gained De perylenetetracarboxylic dianhydride rete De Dao perylenetetracarboxylic dianhydride and [6,6]-phenyl-C
61The mixture film that methyl butyrate is combined closely; Film thickness monitoring device on the while close observation vacuum evaporation appearance is as the Du De perylenetetracarboxylic dianhydride of institute and [6,6]-phenyl-C
61The thickness of the mixture film that methyl butyrate is combined closely stops plated film when arriving 35 nanometers, wherein ， perylenetetracarboxylic dianhydride and [6,6]-phenyl-C
61The mol ratio of methyl butyrate is 11.6: 1;
(4). need not to take out, then and then on the vacuum evaporation appearance of regulating step (3) the control heating be mounted with [6,6]-phenyl-C
61The electric current of the crucible of methyl butyrate is 1.3～1.6A vapor deposition [6,6]-phenyl-C
61Methyl butyrate makes [6,6]-phenyl-C
61The methyl butyrate vapor deposition is at step (3) gained De perylenetetracarboxylic dianhydride and [6,6]-phenyl-C
61， Zai perylenetetracarboxylic dianhydride and [6,6]-phenyl-C on the mixture film that methyl butyrate is combined closely
61Obtain [6,6]-phenyl-C on the mixture film that methyl butyrate is combined closely
61The methyl butyrate rete; Film thickness monitoring device on the while close observation vacuum evaporation appearance is as gained [6,6]-phenyl-C
61The thickness of methyl butyrate rete stops plated film when arriving 3 nanometers; At this moment just accomplish whole process of plating, obtain film c.
Utilize above-mentioned various catalyst film to carry out the photoelectrocatalysis experiment, specific practice is following:
(1). one can be airtight the quartz reaction container in add 35mM KNO
3As electrolyte, use 1M H
2SO
4Above-mentioned electrolytical pH value furnishing 2.As required, can in above-mentioned electrolyte, add or not add various sacrifice agents.
(2). the argon gas deoxygenation is used in the quartzy bottle back of airtight step (1); And in this quartzy bottle, make up a photoelectrocatalysis battery three-electrode system; Wherein: working electrode is: organic semiconductor film catalyst film a～e light anode, and reference electrode is: calomel electrode to electrode is: platinum electrode; (irradiation of λ＞420nm) down, the connection electrochemical workstation carries out the photoelectrocatalysis decomposition water at visible light; The gas that is produced is used gas chromatographic detection.
Illumination experiment condition a: halogen lamp is placed in the double glazing condensation sleeve pipe, on every side around recirculated cooling water.(λ＞420nm) places the chuck outside to excise the light below the 420nm fully and guarantee that reaction only carries out under visible light for cut-off type optical filter.
Related photoelectrocatalysis experimental procedure and illumination experiment condition are all as stated in following examples.
The photoelectrocatalysis effect of the film of above-mentioned five kinds of different structures is as shown in Figure 1.
Curve a: the photoelectrocatalysis curve of film a.
Curve b: the photoelectrocatalysis curve of film b.
Curve c: the photoelectrocatalysis curve of film c.
Curve d: the photoelectrocatalysis curve of film d.
Curve e: the photoelectrocatalysis curve of film e.
Curve f: film e electro-catalysis curve in the dark.
Curve a among Fig. 1 is visible light (luminous intensity is 110 milliwatt/square centimeters) the irradiation photoelectrocatalysis behavior of film a down, and this shows that Ban Dao Ti perylenetetracarboxylic dianhydride has certain photoelectric catalytically active.Curve b is film b [6,6]-phenyl-C under visible light shines
61The photoelectrocatalysis behavior of methyl butyrate shows [6,6]-phenyl-C
61Methyl butyrate has also shown certain photoelectric catalytically active.Curve c is the photoelectrocatalysis behavior of film c under visible light shines, Biao Ming perylenetetracarboxylic dianhydride and [6,6]-phenyl-C
61The mixture table of methyl butyrate has revealed certain photoelectric catalytically active enhancement effect.Curve d is the photoelectrocatalysis behavior of film d under visible light shines, Biao Ming perylenetetracarboxylic dianhydride and [6,6]-phenyl-C
61The simple duplicature that methyl butyrate is formed does not only have the photoelectric catalytically active enhancement effect, has reduced photoelectric catalytically active on the contrary.Curve e is film e photoelectrocatalysis behavior under visible light shines, Biao Ming perylenetetracarboxylic dianhydride and [6,6]-phenyl-C
61The complicated trilamellar membrane structure that methyl butyrate is formed has increased photoelectric catalytically active greatly.Curve f is the electro-catalysis behavior of film e under the condition of no visible light photograph, and this shows that this complicated trilamellar membrane structure does not have electro catalytic activity, and that is to say does not have illumination, and catalytic decomposition water cannot carry out.
(1) will distinguish Zhuan You perylenetetracarboxylic dianhydride and [6,6]-phenyl-C
61Two quartz containers of methyl butyrate are placed in two crucibles of same vacuum evaporation appearance, above vacuum evaporation appearance cavity, put the electro-conductive glass ITO of 4 * 2cm, are evacuated to 1 * 10 then
-5～4 * 10
-5Pa;
(2). to add the electric current that hot charging carries perylenetetracarboxylic dianhydride's crucible be 1.5A in control on the vacuum evaporation appearance of regulating step (1); add hot perylenetetracarboxylic dianhydride; make perylenetetracarboxylic dianhydride's vapor deposition on electro-conductive glass ITO, one layer of perylenetetracarboxylic dianhydride's rete of plating on electro-conductive glass ITO; Film thickness monitoring device ， on the close observation vacuum evaporation appearance stops plated film when the thickness of perylenetetracarboxylic dianhydride's rete arrives 10 nanometers simultaneously;
(3). need not to take out, then and then on the vacuum evaporation appearance of regulating step (2) control to add the electric current that hot charging carries perylenetetracarboxylic dianhydride's crucible be that 1.5A steams the plating perylenetetracarboxylic dianhydride, regulate simultaneously that the control heating being mounted with [6,6]-phenyl-C on the vacuum evaporation appearance
61The electric current of the crucible of methyl butyrate is 1.6A vapor deposition [6,6]-phenyl-C
61Methyl butyrate ， Shi perylenetetracarboxylic dianhydride and [6,6]-phenyl-C
61Methyl butyrate simultaneously vapor deposition on ， Zai perylenetetracarboxylic dianhydride rete on step (2) the gained De perylenetetracarboxylic dianhydride rete De Dao perylenetetracarboxylic dianhydride and [6,6]-phenyl-C
61The mixture film that methyl butyrate is combined closely; Film thickness monitoring device on the while close observation vacuum evaporation appearance is as the Du De perylenetetracarboxylic dianhydride of institute and [6,6]-phenyl-C
61The thickness of the mixture film that methyl butyrate is combined closely stops plated film when arriving 25 nanometers, wherein ， perylenetetracarboxylic dianhydride and [6,6]-phenyl-C
61The mol ratio of methyl butyrate is 4: 1;
(4). need not to take out, then and then on the vacuum evaporation appearance of regulating step (3) the control heating be mounted with [6,6]-phenyl-C
61The electric current of the crucible of methyl butyrate is 1.3A vapor deposition [6,6]-phenyl-C
61Methyl butyrate makes [6,6]-phenyl-C
61The methyl butyrate vapor deposition is at step (3) gained De perylenetetracarboxylic dianhydride and [6,6]-phenyl-C
61， Zai perylenetetracarboxylic dianhydride and [6,6]-phenyl-C on the mixture film that methyl butyrate is combined closely
61Obtain [6,6]-phenyl-C on the mixture film that methyl butyrate is combined closely
61The methyl butyrate rete; Film thickness monitoring device on the while close observation vacuum evaporation appearance is as gained [6,6]-phenyl-C
61The thickness of methyl butyrate rete stops plated film when arriving 8 nanometers; At this moment just accomplish whole process of plating.
Utilize above-mentioned catalyst film to carry out photoelectrocatalysis experiment, find on working electrode, to add the bias voltage of 0.8V, under visible light illumination (λ＞420nm, luminous intensity is 110 Bos watt/square centimeter), photoelectric current reaches 70 μ Acm
-2
(1) will distinguish Zhuan You perylenetetracarboxylic dianhydride and [6,6]-phenyl-C
61Two quartz containers of methyl butyrate are placed in two crucibles of same vacuum evaporation appearance, above vacuum evaporation appearance cavity, put the electro-conductive glass ITO of 4 * 2cm, are evacuated to 1 * 10 then
-5～4 * 10
-5Pa;
(2). to add the electric current that hot charging carries perylenetetracarboxylic dianhydride's crucible be 1.8A in control on the vacuum evaporation appearance of regulating step (1); add hot perylenetetracarboxylic dianhydride; make perylenetetracarboxylic dianhydride's vapor deposition on electro-conductive glass ITO, one layer of perylenetetracarboxylic dianhydride's rete of plating on electro-conductive glass ITO; Film thickness monitoring device ， on the close observation vacuum evaporation appearance stops plated film when the thickness of perylenetetracarboxylic dianhydride's rete arrives 30 nanometers simultaneously;
(3). need not to take out, then and then on the vacuum evaporation appearance of regulating step (2) control to add the electric current that hot charging carries perylenetetracarboxylic dianhydride's crucible be that 1.8A steams the plating perylenetetracarboxylic dianhydride, regulate simultaneously that the control heating being mounted with [6,6]-phenyl-C on the vacuum evaporation appearance
61The electric current of the crucible of methyl butyrate is 1.6A vapor deposition [6,6]-phenyl-C
61Methyl butyrate ， Shi perylenetetracarboxylic dianhydride and [6,6]-phenyl-C
61Methyl butyrate simultaneously vapor deposition on ， Zai perylenetetracarboxylic dianhydride rete on step (2) the gained De perylenetetracarboxylic dianhydride rete De Dao perylenetetracarboxylic dianhydride and [6,6]-phenyl-C
61The mixture film that methyl butyrate is combined closely; Film thickness monitoring device on the while close observation vacuum evaporation appearance is as the Du De perylenetetracarboxylic dianhydride of institute and [6,6]-phenyl-C
61The thickness of the mixture film that methyl butyrate is combined closely stops plated film when arriving 45 nanometers, wherein ， perylenetetracarboxylic dianhydride and [6,6]-phenyl-C
61The mol ratio of methyl butyrate is 7: 1;
(4). need not to take out, then and then on the vacuum evaporation appearance of regulating step (3) the control heating be mounted with [6,6]-phenyl-C
61The electric current of the crucible of methyl butyrate is 1.6A vapor deposition [6,6]-phenyl-C
61Methyl butyrate makes [6,6]-phenyl-C
61The methyl butyrate vapor deposition is at step (3) gained De perylenetetracarboxylic dianhydride and [6,6]-phenyl-C
61， Zai perylenetetracarboxylic dianhydride and [6,6]-phenyl-C on the mixture film that methyl butyrate is combined closely
61Obtain [6,6]-phenyl-C on the mixture film that methyl butyrate is combined closely
61The methyl butyrate rete; Film thickness monitoring device on the while close observation vacuum evaporation appearance is as gained [6,6]-phenyl-C
61The thickness of methyl butyrate rete stops plated film when arriving 15 nanometers; At this moment just accomplish whole process of plating.
Utilize above-mentioned catalyst film to carry out the photoelectrocatalysis experiment, find on working electrode, to add the bias voltage of 0.8V, under visible light illumination (λ＞420nm, luminous intensity is 110 milliwatt/square centimeters), photoelectric current reaches 80 μ Acm
-2
(irradiation of the λ＞420nm) process of the full decomposition water generation hydrogen of photoelectrocatalysis and oxygen down is as shown in Figure 2, and (film e) adds the bias voltage of 0.8V on the working electrode at visible light for catalyst film e among the embodiment 1.
Curve 1: the production process of hydrogen under the radiation of visible light.
Curve 2: the production process of oxygen under the radiation of visible light.
Curve 3: do not have catalyst film e under the radiation of visible light, when having only electro-conductive glass ITO under the bias voltage of 0.8V the generative process of hydrogen and oxygen.
Embodiment 5
The photoelectrocatalysis behavior of catalyst film e under the existence condition of sacrifice agent (hole trapping agents) used among the embodiment 1 is as shown in Figure 3.
Curve 1: add 1.25mM Na
2S is as sacrifice agent, the photoelectrocatalysis behavior of film e when adding the 0.6V bias voltage.
Curve 2: add 5mM KI as sacrifice agent, the photoelectrocatalysis behavior of film e when adding the 0.8V bias voltage.
Curve 3: do not have sacrifice agent (having only water), the photoelectrocatalysis behavior of film e when adding the 0.8V bias voltage.
Curve 4: add 5mM KI as sacrifice agent, the photoelectrocatalysis behavior of electro-conductive glass ITO when adding the 0.8V bias voltage
Embodiment 6
Catalyst film e used among the embodiment 1 is the fastest at the formation speed that hydrogen in the presence of the 1.25mM vulcanized sodium is arranged, and has reached 5.26 μ mol in 2500 second time, and turn over number (total amount of hydrogen is divided by the total amount of catalyst) has reached 318.Other turn over number and condition are as shown in the table:
Embodiment 7
The photoelectrocatalysis behavior of catalyst film e in the presence of 5mM KI used among the embodiment 1 is as shown in Figure 4.Through reusing 3 times, catalyst activity has no conspicuousness to change, and particularly in the 3rd circulation, has carried out the test of turning on light and turning off the light, and shows that as long as illumination stops the photoelectrocatalysis reaction stops to carry out immediately.
Embodiment 8
The electricity conversion of catalyst film e in the photoelectrocatalysis reaction tank used among the embodiment 1 is as shown in Figure 5, and electricity conversion reached the highest when the electricity conversion result was presented at 435 nanometers, reached 1.23%.
Embodiment 9
N, N '-Zheng Wu Ji perylene tetramethyl acid imide [6,6]-phenyl-C
61Methyl butyrate, Me are methyl
Use above-mentioned N, N '-Zheng Wu Ji perylene tetramethyl acid imide and [6,6]-phenyl-C
61Methyl butyrate is made the photo-anode membrane material according to the preparation method of film e plated film among the embodiment 1.Concrete grammar is following:
The adjusting electric current is 1.6A, and plating one layer thickness is the N of 20 nanometers earlier on electro-conductive glass ITO, the inferior acid amides film of the basic perylene tetramethyl of N '-positive penta, and regulating electric current then respectively is 1.6A and 1.3A while vapor deposition N, the basic perylene tetramethyl acid imide of N '-positive penta and [6,6]-phenyl-C
61(thickness of this one deck is 35 nanometers to methyl butyrate, N, the basic perylene tetramethyl acid imide of N '-positive penta and [6,6]-phenyl-C
61The mol ratio of methyl butyrate is 11.6: 1), plate [6,6]-phenyl-C that a layer thickness is 3 nanometers at last again
61Methyl butyrate, gross thickness are 58 nanometers.This has just accomplished the preparation of visible light photoelectrocatalysis agent.
Utilize this catalyst as the light anode in the condition described in the embodiment 1,5mM KI is as sacrifice agent, the 0.8V bias voltage has produced 3.1 micromolar hydrogen in 2500 seconds time.
Comparative Examples 1
(irradiation of λ＞420nm) produces heat and the thermal response that causes, carried out the dark reaction of catalyst (catalyst film e among the embodiment 1) photoelectrocatalysis decomposition water in 40 ℃ of water-baths in order to get rid of visible light.Experimental result shows: under the dark reaction condition of heating, catalyst does not have catalytic activity, and dark current is very little, and does not have the generation of hydrogen and oxygen.In the reaction time, can get rid of the generation that is caused water decomposition or hydrogen by thermal response basically thus, promptly the generation of the decomposition of water or hydrogen is that photocatalytic activity by catalyst according to the invention causes fully in the reaction time internal reaction system.
Comparative Examples 2
In order to obtain optimized photoelectrocatalysis experiment condition, carried out a series of contrast test.
Condition one: one can be airtight the quartz reaction container in add 15mM KNO
3As electrolyte, use 1M H
2SO
4Above-mentioned electrolytical pH value furnishing 1.
Condition two: one can be airtight the quartz reaction container in add 15mM KNO
3As electrolyte, use 1M H
2SO
4Above-mentioned electrolytical pH value furnishing 2.
Condition three: one can be airtight the quartz reaction container in add 15mM KNO
3As electrolyte, use 1M H
2SO
4Above-mentioned electrolytical pH value furnishing 3.
Condition four: one can be airtight the quartz reaction container in add 35mM KNO
3As electrolyte, use 1M H
2SO
4Above-mentioned electrolytical pH value furnishing 1.
Condition five: one can be airtight the quartz reaction container in add 35mM KNO
3As electrolyte, use 1M H
2SO
4Above-mentioned electrolytical pH value furnishing 2.
Condition six: one can be airtight the quartz reaction container in add 35mM KNO
3As electrolyte, use 1M H
2SO
4Above-mentioned electrolytical pH value furnishing 3.
Condition seven: one can be airtight the quartz reaction container in add 55mM KNO
3As electrolyte, use 1M H
2SO
4Above-mentioned electrolytical pH value furnishing 1.
Condition eight: one can be airtight the quartz reaction container in add 55mM KNO
3As electrolyte, use 1M H
2SO
4Above-mentioned electrolytical pH value furnishing 2.
Condition nine: one can be airtight the quartz reaction container in add 55mM KNO
3As electrolyte, use 1M H
2SO
4Above-mentioned electrolytical pH value furnishing 3.
Catalyst film e used among the embodiment 1 put into above-mentioned various experiment conditions can be airtight the quartz reaction container in; Use the argon gas deoxygenation; And in this quartzy bottle, make up a photoelectrocatalysis battery three-electrode system; Wherein: working electrode is: organic semiconductor film catalyst light anode, and reference electrode is: calomel electrode to electrode is: platinum electrode; (irradiation of λ＞420nm) down, the connection electrochemical workstation carries out the photoelectrocatalysis decomposition water at visible light;
Illumination experiment condition a: halogen lamp is placed in the double glazing condensation sleeve pipe, on every side around recirculated cooling water.(λ＞420nm) places the chuck outside to excise the light below the 420nm fully and guarantee that reaction only carries out under visible light for cut-off type optical filter.
Under the bias voltage of 0.8V, the result is following:
Condition one: photoelectric current is 77 μ Acm
-2
Condition two: photoelectric current is 87 μ Acm
-2
Condition three: photoelectric current is 66 μ Acm
-2
Condition four: photoelectric current is 58 μ Acm
-2
Condition five: photoelectric current is 110 μ Acm
-2
Condition six: photoelectric current is 90 μ Acm
-2
Condition seven: photoelectric current is 37 μ Acm
-2
Condition eight: photoelectric current is 83 μ Acm
-2
Condition nine: photoelectric current is 45 μ Acm
-2
Condition ten: photoelectric current is 55 μ Acm
-2
Can find out that optimum experiment condition is the condition among the embodiment 1: 35mM KNO
3As electrolyte, use 1M H
2SO
4Above-mentioned electrolytical pH value furnishing 2.
Claims (4)
1. the organic semiconductor visible-light photocatalyst of a membrane structure, it is characterized in that it is made up of trilamellar membrane, ground floor: perylene diimide derivative rete, the thickness of rete are 10～30 nanometers; Second layer: perylene diimide derivative and [6,6]-phenyl-C
61The mixture film of methyl butyrate, the thickness of rete are 25～45 nanometers, wherein ， perylene diimide derivative and [6,6]-phenyl-C
61The mol ratio of methyl butyrate is 4: 1～11.6: 1; The 3rd layer: [6,6]-phenyl-C
61Methyl butyrate rete, the thickness of rete are 3～15 nanometers;
The structure of Suo Shu De perylene diimide derivative is:
Wherein: R, R ' are C independently
20Following aliphatic hydrocarbon substituting group;
Described [6,6]-phenyl-C
61The structure of methyl butyrate is:
Wherein Me is a methyl.
2. the preparation method of the organic semiconductor visible-light photocatalyst of a membrane structure according to claim 1 is characterized in that, this method may further comprise the steps:
(1). will adorn perylene diimide derivative and [6,6]-phenyl-C respectively
61Two quartz containers of methyl butyrate are placed in two crucibles of same vacuum evaporation appearance, above vacuum evaporation appearance cavity, put electro-conductive glass ITO, are evacuated to 1 * 10 then
-5～4 * 10
-5Pa;
(2). to add the electric current that hot charging carries the crucible of perylene diimide derivative be 1.5～1.8A in control on the vacuum evaporation appearance of regulating step (1); add hot perylene diimide derivative; make perylene diimide derivative vapor deposition on electro-conductive glass ITO; must arrive perylene diimide derivative rete, when thickness arrival 10～30 nanometers of perylene diimide derivative rete, stops plated film;
(3). then and then on the vacuum evaporation appearance of regulating step (2) control to add the electric current that hot charging carries the crucible of perylene diimide derivative be that 1.5～1.8A steams plating perylene diimide derivative, regulate simultaneously that the control heating being mounted with [6,6]-phenyl-C on the vacuum evaporation appearance
61The electric current of the crucible of methyl butyrate is 1.3～1.6A vapor deposition [6,6]-phenyl-C
61Methyl butyrate ， Shi perylene diimide derivative and [6,6]-phenyl-C
61Methyl butyrate vapor deposition simultaneously must arrive perylene diimide derivative and [6,6]-phenyl-C on perylene diimide derivative rete on the perylene diimide derivative rete of step (2) gained
61The mixture film of methyl butyrate is as the Du De of institute perylene diimide derivative and [6,6]-phenyl-C
61The thickness of the mixture film of methyl butyrate stops plated film, wherein ， perylene diimide derivative and [6,6]-phenyl-C when arriving 25～45 nanometers
61The mol ratio of methyl butyrate is 4: 1～11.6: 1;
(4). then and then on the vacuum evaporation appearance of regulating step (3) the control heating be mounted with [6,6]-phenyl-C
61The electric current of the crucible of methyl butyrate is 1.3～1.6A vapor deposition [6,6]-phenyl-C
61Methyl butyrate makes [6,6]-phenyl-C
61The methyl butyrate vapor deposition is at step (3) gained De perylene diimide derivative and [6,6]-phenyl-C
61， Zai perylene diimide derivative and [6,6]-phenyl-C on the mixture film of methyl butyrate
61Obtain [6,6]-phenyl-C on the mixture film of methyl butyrate
61The methyl butyrate rete is as gained [6,6]-phenyl-C
61The thickness of methyl butyrate rete stops plated film when arriving 3～15 nanometers, obtains the organic semiconductor visible-light photocatalyst of described membrane structure;
The structure of Suo Shu De perylene diimide derivative is:
Wherein: R, R ' are C independently
20Following aliphatic hydrocarbon substituting group;
Described [6,6]-phenyl-C
61The structure of methyl butyrate is:
Wherein Me is a methyl.
3. the application of the organic semiconductor visible-light photocatalyst of a membrane structure according to claim 1; It is characterized in that: the organic semiconductor visible-light photocatalyst of described membrane structure is used for splitting water into hydrogen and oxygen exciting under the synergy with electric field of visible light.
4. application according to claim 3 is characterized in that: the described method that splits water into hydrogen and oxygen under the synergy with electric field that excites at visible light is:
(1). one can be airtight the quartz reaction container in add 15～55mM KNO
3As electrolyte, use 1M H
2SO
4Above-mentioned electrolytical pH value furnishing 1～3;
(2). use the inert gas deoxygenation behind the quartz reaction container of airtight step (1); And in this quartz reaction container, make up a photoelectrocatalysis battery three-electrode system; Wherein: working electrode is: the organic semiconductor visible-light photocatalyst light anode of membrane structure; Reference electrode is: calomel electrode to electrode is: platinum electrode; Under radiation of visible light, connect electrochemical workstation and carry out the photoelectrocatalysis decomposition water.
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| CN108004564A (en) * | 2017-11-29 | 2018-05-08 | 中国矿业大学 | Semiconductor photoelectrode photocatalytic water reaction unit and preparation method based on black silicon PN junction |
| CN110305328B (en) * | 2018-06-19 | 2022-03-04 | 常熟理工学院 | Dendritic visible light initiator and preparation method and application thereof |
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