CN103360429B - Cyclometalated iridium photosensitizers, synthesis and go out the application of hydrogen at photo catalytic reduction water - Google Patents
Cyclometalated iridium photosensitizers, synthesis and go out the application of hydrogen at photo catalytic reduction water Download PDFInfo
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- CN103360429B CN103360429B CN201310312808.9A CN201310312808A CN103360429B CN 103360429 B CN103360429 B CN 103360429B CN 201310312808 A CN201310312808 A CN 201310312808A CN 103360429 B CN103360429 B CN 103360429B
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- iridium photosensitizers
- iridium
- hydrogen
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Abstract
The invention discloses a kind of Cyclometalated iridium photosensitizers, synthesis and application thereof.The synthesis of iridium photosensitizers comprises: by chlorine bridge dimer [Ir (tfmppy) (μ-Cl)]
2be placed in the mixed solvent of methyl alcohol and methylene dichloride with bisbenzimidazole, add Na
2cO
3, back flow reaction; Reaction terminates rear cooling, be spin-dried for solvent after cross post and obtain target product, crossing post developping agent ratio is ethyl acetate: normal hexane=1:1 is to pure ethyl acetate.Method of the present invention can obtain monokaryon and double-core iridium photosensitizers simultaneously, and its aftertreatment is simple, just can obtain pure product by simple column method of crossing.Compared with preparing hydrogen with traditional monokaryon iridium photosensitizers photo catalytic reduction water, monokaryon iridium photosensitizers of the present invention, still possesses good photo catalytic reduction water and goes out hydrogen performance; Double-core iridium photosensitizers of the present invention has higher activity compared with monokaryon iridium photosensitizers simultaneously.
Description
Technical field
The present invention relates to a kind of iridium photosensitizers, synthesis and go out the application of hydrogen at photo catalytic reduction water, belong to chemical industry energy field.
Background technology
The consumption of fossil energy not only causes energy dilemma, simultaneously also seriously destroys the environment that we survive day by day.Searching is cleaned, and reproducible new forms of energy carry out the focus that alternative fossil energy becomes current research.Hydrogen, as environmental protection, the secondary energy carrier of clean energy, receives the concern of people day by day.But so far, preparing the main method of hydrogen, is still by water electrolysis is resolved into hydrogen, and the greatest drawback of this method is to consume a large amount of electric energy, and the electric energy consumed is greater than obtained Hydrogen Energy, loses more than gain.And find energy-conservation mode and split water into the focus that hydrogen and oxygen just become research.
1972, Japanese Scientists Fujishima delivered one section and utilizes TiO on Nature
2semi-conductor, under the action of uv light, resolves into hydrogen and oxygen by pure water, started the brand-new field of photochemical catalyzing.After this, there has been significant progress in photochemical catalyzing field, derives two fields: homogeneous photochemical catalysis water of decomposition and Heterogeneous photocatalysis water of decomposition.Heterogeneous photocatalysis water of decomposition goes out hydrogen field at present at China's focus utilization semiconductor material, but semiconductor material is poor for the receptivity of visible ray, simultaneously its catalytic rate feature slowly.And homogeneous photochemical catalysis system not only to have hydrogen production conversion efficiency high, and the performance of photosensitizers can be changed greatly by the modification of part and receive the concern of extensive researcher.Such as U.S. Stefan Bernhard seminar, at J. Am. Chem. Soc., Inorg. Chem., Chem. Eur. J., the internationally famous periodicals such as Chem. Commun is delivered with [Ir (C^N)
2(N^N)]
+positively charged ion iridium photosensitizers based on formula.In its formula, C^N part can just like Types Below, and N^N part can have as follows:
,
2009, Stefan Bernhard seminar delivered the iridium photosensitizers based on C^N^N first on Inorg. Chem, and its structure is as follows, and this photosensitizers has high stability, but it has active not high shortcoming simultaneously.
But up to now, the exploitation for iridium photosensitizers concentrates on monokaryon iridium photosensitizers, and the photosensitive exploitation of double-core iridium there is not yet bibliographical information.
Summary of the invention
The object of the present invention is to provide a kind of Cyclometalated iridium photosensitizers, is a kind of photosensitizers that fast water preparation can be reduced into hydrogen.
Another object of the present invention is to provide the synthetic method of described iridium photosensitizers, utilizes nuclear-magnetism simultaneously, and mass spectrum carries out structural characterization to material.
Another object of the present invention is to provide and utilizes above-mentioned iridium photosensitizers to realize visible light photocatalytic reduction of water at different conditions to prepare hydrogen.
A kind of Cyclometalated iridium photosensitizers, described iridium photosensitizers, structure is as follows:
P1 (double-core) P2(monokaryon)
The chemical formula of above-mentioned iridium photosensitizers is Ir (tfmppy) (BiBzIm) Ir (tfmppy) (P1), Ir (tfmppy)
2(BiBzImH) (P2), wherein tfmppy is 4-trifluoromethylbenzene pyridine, and BiBzIm is bisbenzimidazole.
A synthesis for iridium photosensitizers, comprises the following steps:
The first step, by chlorine bridge dimer [Ir (tfmppy) (μ-Cl)]
2be placed in the mixed solvent of methyl alcohol and methylene dichloride with bisbenzimidazole, add Na
2cO
3, back flow reaction;
Second step, reaction terminate rear cooling, be spin-dried for solvent after cross post and obtain target product, crossing post developping agent ratio is ethyl acetate: normal hexane=1:1 is to pure ethyl acetate.
The mol ratio of the chlorine bridge dimer described in the first step and bisbenzimidazole is 1:2.2.
The volume ratio of the methyl alcohol described in the first step and methylene dichloride is 1:1.
Na described in the first step
2cO
3be 1:10 with the dimeric mol ratio of chlorine bridge.
Reaction times described in the first step is greater than 20h.
A kind of iridium photosensitizers prepared according to above-mentioned synthetic method is applied in visible light photocatalytic reduction of water and goes out in hydrogen, by iridium photosensitizers, electronics sacrifice agent trolamine and CATALYST Co (bpy)
3 2+, K
2ptCl
4, CoCl
2or Rh (dtbpy)
3 3+and LiCl dissolves in aqueous, with concentrated hydrochloric acid, pH value is adjusted to 8, under the irradiation of visible ray, photo catalytic reduction water prepares hydrogen.
The invention has the beneficial effects as follows:
1. can obtain monokaryon and double-core iridium photosensitizers by synthetic method disclosed in the present invention, and its aftertreatment is simple simultaneously, just can obtains pure product by simple column method of crossing.
2., compared with preparing hydrogen with traditional monokaryon iridium photosensitizers photo catalytic reduction water, monokaryon iridium photosensitizers of the present invention, still possesses good photo catalytic reduction water and goes out hydrogen performance.
3. double-core iridium photosensitizers of the present invention has higher activity compared with monokaryon iridium photosensitizers.
Accompanying drawing explanation
Fig. 1 is the nucleus magnetic hydrogen spectrum figure (a is P1, b is P2) of the embodiment of the present invention 1.
Embodiment
The synthesis of embodiment 1:P1 and P2
Hydrated iridium trichloride and 4-trifluoromethylbenzene pyridine are joined 40 ml ethylene glycol monoethyl ethers in 1:2.2 ratio: in water=3:1; under nitrogen protection; 24h is reacted under 140 DEG C of conditions; by reaction solution cool to room temperature after reaction terminates; add 100 ml deionized waters, now can separate out a large amount of yellow solids.Reaction solution is obtained yellow solid by filtration under diminished pressure.With methylene dichloride, yellow solid is dissolved again, by ethyl acetate: normal hexane=1:1 crosses post, collect yellow liquid, obtain pure chlorine bridge dimer [Ir (tfppy) (μ-Cl)]
2.
By chlorine bridge dimer [Ir (tfppy) (μ-Cl)]
2(300 mg) and bisbenzimidazole (128.7mg) join mixed solvent C H in the ratio of 1:2.2
2cl
2: CH
3in OH=1:1, add Na
2cO
3be 396 mg; back flow reaction 24 hours under nitrogen protection condition at 70 DEG C; after reaction terminates; cool to room temperature; be spin-dried for reaction solvent and cross pillar; the ratio of developping agent is ethyl acetate: normal hexane=1:1 crosses post to ethyl acetate, successively obtains double-core iridium photosensitizers Ir (tfppy) (BiBzIm) Ir (tfppy) Cl
2(P1) 82 mg and monokaryon iridium photosensitizers Ir (tfppy) (BiBzImH) (P2) 182 mg.We are successively by nucleus magnetic resonance, and mass spectrum is determined its structure.
P1:
1H NMR (DMSO, 500 MHz): δ 8.39 (4H, d, J = 8.2), δ 8.11 (4H, d, J = 8.2), δ 7.97 (4H, t, J= 7.8), δ 7.62 (4H, d, J = 5.7), δ 7.38 (4H, t, J = 8.0), δ 7.15 (4H, t, J = 6.6), δ 6.66 (4H, m), δ 6.61 (4H, s), δ 5.87 (4H, m, J = 3.1). ESI-MS (CH
3OH): 1507.08 [M]
+.
P2:
1H NMR (DMSO, 500 MHz): δ 8.33 (2H, d, J = 8.2), δ 8.13 (2H, d, J = 8.2), δ 7.90 (2H, t, J= 7.4), δ 7.76 (2H, d, J = 5.5), δ 7.56 (2H, d, J = 8.1), δ 7.38 (2H, d, J = 7.9), δ 7.25 (2H, t, J = 6.6), δ 7.08 (2H, t, J = 7.6), δ 6.78 (2H, t, J = 7.6), δ 6.61 (2H, s), δ 5.89 (2H, d, J = 8.3). ESI-MS (CH
3OH): 871.42 [M]
+, 869.42 [M]
-.
HR-MS (CH
3OH): 871.1635.
Embodiment 2
In homogeneous photochemical catalysis system, iridium photosensitizers photo catalytic reduction water prepares hydrogen: by 1 ml 1mol/L iridium photosensitizers P1 or P2,2.5 ml trolamines, 0.33 mM catalyzer, 1 g LiCl, 0.75 ml concentrated hydrochloric acid joins in 100 ml solvents (in solvent acetone: water=4:1), drained by air in reactor, under 300 W xenon lamps irradiate (λ > 420 nm), the hydrogen that reaction generates is through chromatogram ration analysis.It is as shown in table 1 that photosensitizers used goes out hydrogen amount under different catalysts effect:
Table 1
From chart, in these four kinds of catalyzer, except CoCl
2outward, other catalyzer combine with photosensitizers used and all have the ability that catalytic reduction water goes out hydrogen.In the water reducing catalyst of numerous use, Rh (dtbpy)
3 3+best results.
Claims (2)
1. Cyclometalated iridium photosensitizers goes out the application in hydrogen at visible light photocatalytic reduction of water, it is characterized in that described iridium photosensitizers structure is as follows:
2. application according to claim 1, is characterized in that iridium photosensitizers, electronics sacrifice agent trolamine and CATALYST Co (bpy)
3 2+, K
2ptCl
4, CoCl
2or Rh (dtbpy)
3 3+and LiCl dissolves in aqueous, with concentrated hydrochloric acid, pH value is adjusted to 8, under the irradiation of visible ray, photo catalytic reduction water prepares hydrogen.
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| CN109422654B (en) * | 2017-08-21 | 2021-09-28 | 南京理工大学 | Method for synthesizing fatty aminomethylated compounds |
| CN108017675B (en) * | 2017-11-17 | 2021-02-19 | 浙江工业大学 | Binuclear organic metal complex, and light-emitting device and application thereof |
| CN107892704B (en) * | 2017-11-17 | 2021-02-19 | 浙江工业大学 | Multidentate binuclear ring metal complex and device containing same |
| CN111269270B (en) * | 2020-02-28 | 2022-06-21 | 江苏大学 | Neutral bimetallic complex iridium-bis-benzimidazole crystal material and preparation method and application thereof |
| CN111910431B (en) * | 2020-08-11 | 2021-07-02 | 中国科学院长春应用化学研究所 | Metal iridium-based composite material, preparation method thereof and photocatalytic hydrolysis method |
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| CN102408449A (en) * | 2011-09-14 | 2012-04-11 | 中科院广州化学有限公司 | Iridium-containing coordination compound responsive to fluorine ion as well as preparation method and application thereof |
| WO2012074111A1 (en) * | 2010-12-02 | 2012-06-07 | 宇部興産株式会社 | Binuclear metal complex, and organic electroluminescence element using same |
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| CN102408449A (en) * | 2011-09-14 | 2012-04-11 | 中科院广州化学有限公司 | Iridium-containing coordination compound responsive to fluorine ion as well as preparation method and application thereof |
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| 系列2-苯基喹啉类铱配合物的合成及电化学发光性能研究;童碧海、梅群波等;《化学学报》;20121231;2451-2456 * |
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