CN103204882B - A kind of poly-benzimidazole iron complex, its preparation method and application thereof - Google Patents
A kind of poly-benzimidazole iron complex, its preparation method and application thereof Download PDFInfo
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Abstract
The present invention relates to one not anion-containing neutral poly-benzimidazole ferrous metal title complex, its preparation method and application.The present invention also provides the method for the EDTB part that a kind of purity obtaining high yield is high, with metal cations Fe
2+or Fe
3+for the source of metallic iron, the iron complex that synthesis is neutral, adopts the method for solvent evaporates to obtain the crystal of metal complexes, collects crystal data show that this title complex belongs to oblique system, C2/c spacer through monocrystalline X-ray.This title complex, in neutral water, catalytic water decomposition can discharge oxygen under the visible light-inducing of 370nm-750nm, can as the catalyzer of water decomposition.
Description
Technical field
The present invention relates to the catalyzer that a kind of novel photocatalytic water splitting releases oxygen.Particularly, the present invention relates to one not anion-containing poly-benzimidazole iron complex, its preparation method and application thereof.More specifically, the present invention relates to a kind of monoclinic structure not containing negatively charged ion iron complex, can be used as the catalyzer that visible light-inducing catalytic water is decomposed.。
Background technology
Sun power is a kind of inexhaustible, nexhaustible, and the novel energy of cleanliness without any pollution.Along with the utilization and exploitation to solar energy resources, decomposing water with solar energy oxygen can be utilized and to convert solar energy into electrical energy or chemical energy becomes a study hotspot.But in the catalyzer of current most catalytic water cracking, general employing noble metal Ru and Ir, expensive, unfriendly to environment, and adopt the compound (Ce (NH containing tetravalence Ce
4)
2(NO
3)
6) as artificial oxidation's agent of sacrificial.So researchist wishes to find the not only cheap but also catalytic material of environmental protection to replace precious metal, reach the object of splitting water.Cheap metallic iron and the title complex of manganese cause the extensive concern of people.
Nitrogenous a metal-organic complex has novel structure and in catalysis, electrochemistry, absorption, anionresin and magnetic aspect have potential using value.In addition, as a kind of novel functional molecular material, coordination compound has the characteristic of the incomparable structure sanction property of other material and easy functionalization, the research of this compounds more and more causes the great interest of people, cause inorganic chemistry, coordination chemistry, the extensive attention of the aspect such as Organometallic Chemistry and bio-inorganic chemistry investigator.N, N, N', N'-tetra-(2-benzoglyoxaline methylene radical)-1，2-diaminoethane (EDTB) has ten potential coordination atom N, and energy and metal form the title complex of monokaryon or double-core, what these title complexs had demonstrates catalytic activity, the model compound that can be used as enzyme had.The metal complexes of open poly-benzimidazole class in application number 200910272804.6, it is used as non-viral gene vector, prior art (Guiling Wu, etal.Dalton Trans., 2011,40,6433) metal complexes of poly-benzimidazole is openly utilized to carry out simulated fat oxydase in.
Summary of the invention
The present inventor adopts the metallic iron title complex containing poly-benzimidazole to be used as the catalyzer of catalytic water decomposition.Wherein, utilize cheap metal iron to synthesize a kind of not anion-containing title complex newly, this title complex can catalytic water decompose, at present there are no the report of pertinent literature under the induction of visible ray.
The object of the invention is to synthesize a kind of catalystic material decomposed as catalytic water, a kind of not anion-containing poly-benzimidazole ferrous metal title complex of neutrality, and the preparation method and application of this metal complexes.The present invention also provides the method for the crystalline structure having cultivated this metal complexes.The present invention also provides part N simultaneously, the preparation method of N, N', N'-tetra-(2-benzoglyoxaline methylene radical)-1，2-diaminoethane (EDTB).
The present invention is achieved through the following technical solutions:
(1) the poly-benzimidazole iron complex of formula (I) or a solvate, is characterized in that:
Wherein:
R is C
1-C
6alkyl, preferred C
1-C
3alkyl, such as methyl, ethyl, n-propyl or sec.-propyl,
N is 0-5.
(2) according to title complex or the solvate of (1), it is characterized in that, described solvate is hydrate or alcohol adduct, preferred alcohols compound, more preferably methanol solvate, or ethanolates.Also more preferably 2 molecule methanol solvate.
(3) according to title complex or the solvate of (1) or (2), it is characterized in that, described title complex has following structure:
(4) according to title complex or the solvate of (3), it is characterized in that, be the 2 molecule methanol solvate of formula I-2, described title complex is oblique system, C2/c spacer, and its unit cell parameters is
α=90.00, β=110.50, γ=90.00, Z=16, volume is
(5) according to title complex or the solvate of any one of (1)-(2), it is characterized in that, described title complex has following structure:
Wherein R is C
1-C
6alkyl, preferred C
1-C
3alkyl, such as methyl, ethyl, n-propyl or sec.-propyl.
(6) preparation method of title complex or solvate described in any one of above-mentioned (1)-(5), is characterized in that: poly-benzimidazole part, under molysite exists, reacts acquisition in organic solvent.
(7) according to the preparation method of (6), it is characterized in that, described poly-benzimidazole is the N of following formula (II), N, N', N'-tetra-(2-benzoglyoxaline methylene radical)-1，2-diaminoethane (EDTB):
(8) according to the preparation method of any one of (6)-(7), it is characterized in that, described organic solvent is selected from alcohols, as lower alcohol, and particular methanol, ethanol and propyl alcohol.
(9) according to the preparation method of any one of (6)-(8), it is characterized in that, described temperature of reaction is 10-70 DEG C, preferred 20-60 DEG C, more preferably 30-40 DEG C, 30 minutes-6 hours reaction times, preferred 1-4 hour.(10) according to the preparation method of any one of (6)-(9), it is characterized in that, in reaction process, add alkali.Described alkali preferably contains inorganic salt and the organic salt of hydroxide radical and carbonate or bicarbonate radical, preferred sodium bicarbonate or TBAH.
(11) according to the preparation method of any one of (6)-(10), it is characterized in that, described poly-benzimidazole part is 1:1-2, preferred 1:1-1.05 with the weight/power ratio ratio of molysite, and the add-on of described alkali is 2-3 times of weight part of poly-benzimidazole part.
(12) according to the preparation method of any one of (6)-(11), it is characterized in that, described reaction stirring is carried out, reaction end is filtered, after filtration, after filtrate is left standstill volatilization (preferred a couple of days), obtain the crystal of metal complexes.
(13) according to the preparation method of any one of (6)-(12), it is characterized in that, described molysite is selected from Fe (ClO
4)
3, FeCl
3, FeSO
4deng the salt containing iron ion.
(14) according to the preparation method of any one of (6)-(13), it is characterized in that, described carbonate or supercarbonate are selected from sodium carbonate, salt of wormwood, sodium bicarbonate or saleratus.
(15) poly-benzimidazole of formula (II) is the preparation method of a N, N, N', N'-tetra-(2-benzoglyoxaline methylene radical)-1，2-diaminoethane (EDTB), it is characterized in that,
Synthesized under the displacement of rare gas element is protected by ethylenediamine tetraacetic acid (EDTA) and O-Phenylene Diamine.
(16) according to the method for (15); it is characterized in that; by ethylenediamine tetraacetic acid (EDTA) and O-Phenylene Diamine according to a certain percentage (preferred molar ratio is 1:4); with ethylene glycol (ethylene glycol of preferred deoxygenation) for solvent; under the protection of rare gas element, at 120 DEG C-160 DEG C, stirring reaction 6-12h obtains.
(17) according to the method for (15) or (16), it is characterized in that, described stirring reaction is until anhydrous steam is released, reactant is cooled to about 100 DEG C, filter after adding distilled water, and with a large amount of deionized water drip washing, obtain the blocks of solid of lightpink.
(18) according to the method for any one of (15)-(17), it is characterized in that, also comprise thick product dehydrated alcohol crystallization 2-3 time to lightpink, obtain white powder solid.
(19) catalyzer, it is containing the title complex of any one of with good grounds (1)-(5).
(20) according to the application of the title complex of any one of (1)-(5), it is characterized in that, the described title complex catalyzer that catalytic water is decomposed under visible light-inducing.
(21) according to the cultural method of formula (I) the metal complexes crystal of any one of (1)-(5), it is characterized in that, this metal complexes is by spreading or volatilize or the method cultivation of low temperature obtains.
Detailed description of the present invention
The present inventor finds, benzoglyoxaline part of the present invention, under alcohol organic solvent exists, reacts with molysite and forms iron complex.The present invention also finds crystalline structure and the molecular structure of iron complex, three imidazoles nitrogen of iron and EDTB and the coordination of two alkyl nitrogen, axially also has an alkoxyl group to participate in coordination, forms the octahedral structure of a distortion.Due under the effect of alkali, this metal complexes has sloughed two protons on two imidazole rings, forms neutral metal complexes.In the present invention, when methanol is used as solvent, the complex molecule formula C of solvent-free molecule methyl alcohol
35h
33feN
10o, is formula I-1 structure.And we also find, in reaction process, formula I-1 structure is easily in conjunction with bimolecular methyl alcohol, and form methanol solvate form, be formula I-2 structure, molecular structure is C
35h
33feN
10o2CH
3(molecular formula is C to OH
37h
41feN
10o
3).
Molecular formula of the present invention is C
37h
41feN
10o
3the metal complexes of formula I-2, it is oblique system, and spacer is C2/c, and unit cell parameters is
α=90.00, β=110.50, γ=90.00, Z=16, volume is
crystalline structure is as Fig. 1, and single crystal parameters is as shown in the table:
Table 1: single crystal parameters
The present invention also provides a kind of part N; N; N'; the synthetic method of N'-tetra-(2-benzoglyoxaline methylene radical)-1，2-diaminoethane (EDTB), is characterized in that; by ethylenediamine tetraacetic acid (EDTA) and O-Phenylene Diamine according to a certain percentage (preferred molar ratio is 1:4); with ethylene glycol (ethylene glycol of preferred deoxygenation) for solvent, under the protection of rare gas element, at 120 DEG C-160 DEG C, stirring reaction 6-12h obtains.
According to the present invention, reactant, until anhydrous steam is released, is cooled to about 100 DEG C, filters after adding distilled water, and with a large amount of deionized water drip washing, obtain the blocks of solid of lightpink by described stirring reaction.
According to the present invention, also comprise thick product dehydrated alcohol crystallization 2-3 time to lightpink, obtain white powder solid.
Part synthetic method of the present invention, because react under the protection of rare gas element, productive rate is greatly improved, and can reach more than 95%.
Beneficial effect of the present invention:
The neutral metal iron complex that the present invention obtains can be used as catalyzer, decomposes release oxygen for catalytic water under the induction of visible ray.At present in neutral water, with the catalyzer of visible light-inducing water decomposition there are no relevant bibliographical information.The present invention adopts the method synthetic ligands EDTB of inert gas replacement, and productive rate and purity are improved significantly.
Accompanying drawing explanation
Fig. 1 is the Ortep figure of the embodiment of the present invention 2 metal complexes.In order to view is clear, hydrogen atom and solvent molecule omit.
Fig. 2 is the uv-visible absorption spectra of the embodiment of the present invention 2 ferrous metal title complex.
Fig. 3 is that the water droplet of the embodiment of the present invention 2 ferrous metal title complex determines uv-visible absorption spectra figure.
Fig. 4 is the embodiment of the present invention 2 ferrous metal title complex ultraviolet-visible light spectrogram under visible light illumination.
Fig. 5 is the traffic order regularity figure of the embodiment of the present invention 2 metal complexes.
Embodiment
The present invention is described technical scheme of the present invention by following specific embodiment.But those skilled in the art understand, and these embodiments are not for limiting the present invention, any improvement of making on basis of the present invention and change are all within protection scope of the present invention.
Embodiment 1: part N, the synthesis of N, N', N'-tetra-(2-benzoglyoxaline methylene radical)-1，2-diaminoethane (EDTB)
The ethylene glycol of 100ml is added in two mouthfuls of round-bottomed flasks of 250ml, at room temperature remove dissolved oxygen after inflated with nitrogen 20min, 50mmol ethylenediamine tetraacetic acid (EDTA) and 200mmol O-Phenylene Diamine is added in ethylene glycol, after at room temperature continuing inflated with nitrogen 10min, flask is placed on heated and stirred in the oil bath of 140 DEG C, keeps in the process passing into nitrogen, after reacting about 12h always, system has a large amount of solids to separate out, and the volume of reaction solution reduces.Now stopped reaction, cooling, solution becomes thickness, filters after adding 100ml distilled water, and is colourless with a large amount of distilled water drip washing to filtrate, obtains the thick product of lightpink.After thick product being used the ethyl alcohol recrystallization of more 100ml, obtain white powder solid 27.56g, productive rate is 95%.
Embodiment 2: the synthesis of ferrous metal title complex
By EDTB (1.0mmol, 0.5833g), Fe (ClO
4)
3xH
2o (1.0mmol, 0.3638g), NaHCO
3the round-bottomed flask of 250mL put into by (2.0mmol, 0.1703g) solid, adds 100mL methyl alcohol, after ultrasonic 2 minutes, be placed in the oil bath of 25 DEG C and stir, react after 6 hours and stop heating, filter after naturally cooling to room temperature, filtrate is left standstill, about grow a large amount of red crystals after fortnight.The amount 0.3052g of crystal, productive rate 45.85%.Determine that this metal complexes is C through the analysis of X-ray single crystal diffraction
35h
33feN
10o2CH
3(molecular formula is C to OH
37h
41feN
10o
3), crystalline structure figure is as shown in Figure 1.
Embodiment 3: the synthesis of ferrous metal title complex
By EDTB (1.0mmol, 0.5820g), Fe (ClO
4)
39H
2o (1.0mmol, 0.5203g), NaHCO
3(3.0mmol, 0.2520g) round-bottomed flask of 250mL put into by solid, add 100mL methyl alcohol, after ultrasonic 2 minutes, be placed in the oil bath of 60 DEG C and stir, react after 1 hour and stop heating, filter after naturally cooling to room temperature, filtrate left standstill volatilization or rests in-20 DEG C of refrigerators, separating out a large amount of red crystals after a couple of days, determine that this metal complexes is C through the analysis of X-ray single crystal diffraction
35h
33feN
10o2CH
3(molecular formula is C to OH
37h
41feN
10o
3), crystalline structure is as shown in Figure 1.
Embodiment 4: the synthesis of ferrous metal title complex
By EDTB (0.20mmol, 0.1195g), FeCl
36H
2o (0.20mmol, 0.0541g), NaHCO
3(0.60mmol, 0.0504g) round-bottomed flask put into by solid, adds 30mL methyl alcohol, after ultrasonic 2 minutes, be placed in the oil bath of 40 DEG C and stir, react after 2 hours and stop heating, filter after naturally cooling to room temperature, filtrate is left standstill volatilization, about grow a large amount of red crystals after a couple of days, when thoroughly evaporating into solvent-free by solvent, select suitable monocrystalline crystal, determine that this metal complexes is C through the analysis of X-ray single crystal diffraction
35h
33feN
10o, it has the unit cell parameters identical with the metal complexes in embodiment 3, and its crystalline structure as shown in Figure 1.
Embodiment 5: the synthesis of ferrous metal title complex
By EDTB (0.50mmol, 0.2905g), Fe (SO
4) 7H
2o (0.50mmol, 0.1393g), NaHCO
3(1.0mmol, 0.0844g) put into 40ml methyl alcohol, then reacting by heating stopped reaction after 6 hours in the oil bath of 25 DEG C, by leave standstill after reacting liquid filtering place a couple of days after obtain red crystals, determine that this metal complexes is C through the analysis of X-ray single crystal diffraction
35h
33feN
10o2CH
3(molecular formula is C to OH
37h
41feN
10o
3), crystalline structure is as shown in Figure 1.
Embodiment 6: the synthesis of ferrous metal title complex
By EDTB (1.0mmol, 0.5820g), Fe (ClO
4)
39H
2o (1.0mmol, 0.5203g), NaHCO
3(3.0mmol, 0.2520g) round-bottomed flask of 250mL put into by solid, add 100mL ethanol, after ultrasonic 2 minutes, be placed in the oil bath of 25 DEG C and stir, react after 6 hours and stop heating, filter after naturally cooling to room temperature, filtrate is left standstill volatilization, separates out a large amount of red crystals after a couple of days, determine that this metal complexes is [Fe (C through the analysis of X-ray single crystal diffraction
34h
30n
10) (OCH
2cH
3)].
Embodiment 7: the synthesis of ferrous metal title complex
By EDTB (1.0mmol, 0.5820g), Fe (ClO
4)
39H
2o (1.0mmol, 0.5203g), NaHCO
3(3.0mmol, 0.2520g) round-bottomed flask of 250mL put into by solid, add 100mL propyl alcohol, after ultrasonic 3 minutes, be placed in the oil bath of 35 DEG C and stir, react after 4 hours and stop heating, filter after naturally cooling to room temperature, filtrate is left standstill volatilization, separates out a large amount of red crystals after a couple of days, determine that this metal complexes is [Fe (C through the analysis of X-ray single crystal diffraction
34h
30n
10) (OCH
2cH
2cH
3)].
Embodiment 8: the synthesis of ferrous metal title complex
By EDTB (0.50mmol, 0.2905g), Fe (SO
4) 7H
2o (0.50mmol, 0.1393g), NaOH (1.0mmol, 0.040g) put into 60ml Virahol, then in the oil bath of 40 DEG C, reacting by heating stops heating after 4 hours, filter after reaction solution being naturally cooled to room temperature, leave standstill after placing a couple of days and obtain red crystals, determine that this metal complexes is [Fe (C through the analysis of X-ray single crystal diffraction
34h
30n
10) (OCH (CH
3)
2].
Embodiment 9: the synthesis of ferrous metal title complex
By EDTB (0.50mmol, 0.2905g), Fe (SO
4) 7H
2o (0.50mmol, 0.1393g), TBAH (1.0mmol) puts into 50ml ethanol, then in the oil bath of 35 DEG C, reacting by heating stops heating after 5 hours, filter after reaction solution being naturally cooled to room temperature, leave standstill after placing a couple of days and obtain red crystals, determine that this metal complexes is [Fe (C through the analysis of X-ray single crystal diffraction
34h
30n
10) (OCH
2cH
3].
Experimental example 1: the demarcation of uv-vis spectra
The methanol solution 0.8mL of the iron complex of 40 μMs is added in the cuvette of 1mL, using methyl alcohol as reference, ultra-violet absorption spectrum is surveyed in Hitachi U-3900spectrophotometer type ultraviolet-visual spectrometer, uv-vis spectra shows this metal complexes a wide absorption (as Fig. 2) at 450nm place, this peak is attributed to the absorption peak of part to the transfer transport (LMCT) of metal, and this illustrates that this iron complex can absorb visible ray and then be excited.Get volume 880 μ L, the DMF solution of concentration 50 μMs of iron complexes puts into the cuvette of 1mL, adds water survey ultraviolet-visible absorption spectroscopy (as Fig. 3) of 0 μ L, 10 μ L, 20 μ L, 30 μ L, 40 μ L, 60 μ L, 80 μ L volumes respectively.As seen from the figure, in anhydrous DMF, the LMCT peak of iron complex is at 530nm, and along with the increasing of amount adding water, LMCT peak blue shift gradually, occurs isobestic point at 460nm place, illustrates that water and iron complex there occurs reaction.When the DMF solution radiation of visible light containing water of this metal complexes, there is red shift (as Fig. 4) gradually along with the increase of light application time in the absorption peak at 450nm place, illustrate that this iron complex has photolytic activity, photochemical reaction can occur so the neutral compound of this iron can react with water under the induction of light.
Experimental example 2: active mensuration
Adopt hernia lamp source, use spectral filter to obtain the visible ray of 380nm-750nm, Clark-type oxygen electrode measures the traffic order regularity that catalytic water is decomposed.The DMF solution 10uL getting the iron complex of 77mM is added in the deionized water of 1000uL, detects traffic order regularity, by put oxygen graphic representation (Fig. 5) can see only have deionized water time irradiation, the not generation of oxygen; When adding the title complex illumination of this intermediate iron in deionized water, have oxygen to produce instantaneously, putting oxygen speed is 30nmol/ml/min (slope of a curve), illustrates that this metal complexes has catalytic activity, can be used as the catalyzer of water-splitting.
Claims (10)
1. the poly-benzimidazole iron complex of formula (I) or a solvate, is characterized in that:
Wherein:
R is C
1-C
6alkyl,
N is 0-5.
2. title complex according to claim 1 or solvate, is characterized in that, R is selected from methyl, ethyl, n-propyl or sec.-propyl.
3. title complex according to claim 1 or solvate, is characterized in that, described solvate is methanol solvate, ethanolates, or propyl alcohol compound.
4. title complex according to claim 3 or solvate, is characterized in that, described solvate is 2 molecule methanol solvate.
5. according to title complex or the solvate of any one of claim 1-3, it is characterized in that, described title complex or solvate have following structure:
6. title complex according to claim 5 or solvate, is characterized in that, described title complex is monoclinic structure, and it is 2 molecule methanol solvate of formula (I-2), and its unit cell parameters is
α=90.00 °, β=110.50 °, γ=90.00 °, Z=16, volume is
7. a preparation method for title complex or solvate described in any one of claim 1-6, is characterized in that: poly-benzimidazole part, under molysite exists, reacts acquisition in organic solvent.
8. the preparation method of claim 7, is characterized in that, described poly-benzimidazole part is the N of following formula (II), N, N', N'-tetra-(2-benzoglyoxaline methylene radical)-1，2-diaminoethane:
9. a catalyzer for photocatalytic water splitting, its title complex containing with good grounds any one of claim 1-6 or solvate.
10. according to the title complex of any one of claim 1-6 or the application of solvate, it is characterized in that, described title complex or solvate catalytic water under visible light-inducing is decomposed.
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| CN106404931B (en) * | 2016-08-25 | 2019-09-24 | 河池学院 | A kind of detection reagent and its synthetic method of heavy metal ion |
| CN111961091B (en) * | 2020-08-17 | 2023-01-31 | 生态环境部南京环境科学研究所 | Imidazole derivative polybasic aromatic carboxylate iron complex and preparation method and application thereof |
| CN112574219A (en) * | 2021-01-31 | 2021-03-30 | 湖北大学 | Synthesis method of benzimidazolopyrimidinone derivative |
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| CN101705245A (en) * | 2009-11-17 | 2010-05-12 | 华中师范大学 | Non-viral gene vector of poly-benzimidazole metal complex and preparation and application thereof |
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