CN103706400A - Monomolecular catalyst for catalyzing water oxidation and synthetic method thereof - Google Patents

Monomolecular catalyst for catalyzing water oxidation and synthetic method thereof Download PDF

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CN103706400A
CN103706400A CN201310699017.6A CN201310699017A CN103706400A CN 103706400 A CN103706400 A CN 103706400A CN 201310699017 A CN201310699017 A CN 201310699017A CN 103706400 A CN103706400 A CN 103706400A
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CN103706400B (en
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陈秋云
薛娟娟
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Jiangsu University
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Abstract

The invention relates to a monomolecular catalyst for catalyzing water oxidation and a synthetic method thereof, belonging to the technical field of energy chemistry. The monomolecular catalyst for catalyzing water oxidation, provided by the invention, is a cobalt complex, namely a cobalt chloride complex with name of 4-((di(pyridine-2-methylene)amino)methyl)(3,5-dimethyl-1H-pyrrole-2-yl)ketone. The synthetic method comprises the steps of firstly preparing a PPMdpa ligand, then mixing PPMdpa with cobalt chloride, then adding anhydrous ethanol to perform reaction, and performing ether diffusion and filtration to obtain the cobalt chloride complex of 4-((di(pyridine-2-methylene)amino)methyl)(3,5-dimethyl-1H-pyrrole-2-yl)ketone, namely [(PPMdpa)CoCl2]. The complex prepared by the invention can catalyze water oxidation to release oxygen. The preparation method of the monomolecular catalyst disclosed by the invention is relatively low in cost, is suitable for expandable production and provides a new method for application of renewable energy sources.

Description

A kind of unimolecule catalyst and synthetic method thereof of catalysis water oxidation
Technical field
The unimolecule catalyst and the synthetic method thereof that the present invention relates to a kind of catalysis water oxidation, belong to energy technical field of chemistry.
Background technology
Rising in the urgent need to finding new regenerative resource of the variation of global environment and energy demand.Along with the raising energy of scientific and technological level is to continuable future development, for example application of wind energy and solar energy, but storing these energy uses and transports the challenge that the remaining energy becomes huge science and technology as required.The proposition of the molecule energy provides good selection for addressing these problems, because chemical bond can store the energy of high-energy-density.Simulation artificial photosynthesis, utilizing the decomposition of photocatalysis water is chemical energy by light energy conversion, develops oxidation and the reduction of new catalyst water, for Development of Novel oxygen-atom transfer, develops continuable clean energy resource and has great importance
There is the bacterium of catalysis water generates oxygen in occurring in nature, its activated centre is Mn 4caO xbunch, the activity of manual simulation's nature bacterial oxidation enzyme, has designed the complex of the multinuclear of serial catalysis water oxidation, and monokaryon ruthenium water oxidation catalyst (WOC) as synthetic in people such as Sun Licheng has high turn over number and transformation frequency (TON=50,000, TOF=300 s -1) (Wang L, Duan L, Tong LP, Sun LC. Visible light-driven water oxidation catalyzed by mononuclearruthenium complexes. Journal of Catalysis. 2013; 306:129-132.).But what this class catalyst was used is all noble metal, increased the cost of manufacturing solar energy fuel apparatus.Due to showing great attention to of the high people of causing of metallic cobalt price low activity.The highly active Co catalyst (HanA of people's reports such as Nocera; Wu HT; Sun ZJ; Jia HX, DuPW. Facile deposition of nanostructured cobalt oxidecatalysts from molecular cobaloximes for effcientwater oxidation. Phys. Chem. Chem. Phys. 2013; 15:12534-12538.), but the Co catalysts of having reported needs bipyridyl ruthenium as light source in catalysis water oxidizing process, and in use procedure, cost is higher.General artificial light compositing system need to have photosensitive unit, separation of charge unit and the catalysis multielectron transfer unit that efficiency light is caught.How to utilize photoinduced electronic transfer process to realize water efficient oxidation-reduction and remain a challenge.In view of pyrroles's ketone compounds has good optical absorption characteristics in addition-visual field, bipyridine methyl amine transient metal complex has the characteristic in conjunction with oxygen, and the cobalt complex of this class part is expected the catalyst as water oxidation.Here we report compound 4-((bis-(pyridine-2-methylene) amino that a kind of new pyrrole ketone base forms by benzyl and the coupling of bipyridine methyl amine) methyl) (3,5-dimethyl-1H-pyrroles-2-yl) cobalt complex of ketone, as molecular catalyst energy catalysis water, oxidation discharges oxygen to this cobalt complex.
Summary of the invention
The unimolecule catalyst that the oxidation of a kind of catalysis water is provided of the present invention, i.e. a kind of monokaryon cobalt complex, and the synthesis preparation method of this monokaryon cobalt complex is provided, and this catalyst is applied to catalytic oxidation water oxygen.
The invention provides a kind of unimolecule catalyst of catalysis water oxidation, its name is called: 4-((bis-(pyridine-2-methylene) amino) methyl) the cobalt chloride complex of (3,5-dimethyl-1H-pyrroles-2-yl) ketone (is called for short [(PPMdpa) CoCl 2]), its structural formula is as follows:
Figure 2013106990176100002DEST_PATH_IMAGE002
The invention provides the unimolecule catalyst of a kind of catalysis water oxidation, 4-((bis-(pyridine-2-methylene) amino) methyl) preparation method of cobalt chloride complex of (3,5-dimethyl-1H-pyrroles-2-yl) ketone, concrete steps are as follows:
(1) after being mixed with 4-chloromethyl benzoic acid chlorides, 2,4-dimethyl pyrrole adds carrene (CH 2cl 2) reaction;
(2) in mixed system, add successively two (2-picolyl) amine and triethylamine, under nitrogen protection, oil bath refluxes;
(3) reaction finishes the rear saturated brine extracting and washing of using, and water is used dichloromethane extraction, merges organic phase, and anhydrous sodium sulfate drying, revolves and steam solvent, obtains red oil;
(4) red oil is separated through silica gel column chromatography, with eluent ethyl acetate, obtain light yellow viscous liquid, be 4-((bis-(pyridine-2-methylene) amino) methyl) (3,5-dimethyl-1H-pyrroles-2-yl) ketone (being abbreviated as PPMdpa).
(5) after being mixed with cobalt chloride, PPMdpa adds absolute ethyl alcohol reaction, ether diffusion, filter, obtain blue solid, be 4-((bis-(pyridine-2-methylene) amino) methyl) the cobalt chloride complex of (3,5-dimethyl-1H-pyrroles-2-yl) ketone (is called for short [(PPMdpa) CoCl 2]).
Wherein, 2 described in step (1), the mol ratio of 4-dimethyl pyrrole and 4-chloromethyl benzoic acid chlorides is 1:2～2:1, wherein 2, the concentration of 4-dimethyl pyrrole in mixed solution is 1.9-35 mmol/L; Described reaction is 40 ℃ of reaction 2～10h.
Wherein, two (2-picolyl) amine described in step (2) and the mol ratio of 2,4-dimethyl pyrrole are 1:2～2:1; The mol ratio of triethylamine and two (2-picolyl) amine is 4:1～1:4; It is 80 ℃ of 4～16h that reflux that described oil bath refluxes.
Wherein, the mol ratio of the PPMdpa described in step (5) and cobalt chloride is 1:2～2:1; Wherein the concentration of PPMdpa in mixed liquor is 4.8～24 mmol/L; Described reaction is 70 ℃ of reaction 1～6h.
In a more excellent open example of the present invention, in step (1) 2,4-dimethyl pyrrole adds CH after mixing with mol ratio 1:1 ratio with 4-chloromethyl benzoic acid chlorides 2cl 2150 mL, 40 ℃ of reaction 6h.
In a more excellent open example of the present invention, two (2-picolyl) amine described in step (2) and 2,4-dimethyl pyrrole mol ratio 1:1.2, the mol ratio of described triethylamine and two (2-picolyl) amine is 1:1, nitrogen protection, 80 ℃ of oil bath backflow 8h.
In a more excellent open example of the present invention, the PPMdpa described in step (5) adds absolute ethyl alcohol 50 mL after mixing with cobalt chloride mol ratio 1:1.1 ratio, 70 ℃ of reaction 3h.
[(PPMdpa) CoCl that the present invention makes 2], its molecular formula is C 26h 26n 4oCoCl 2, elementary analysis measured value C, 57.79; H, 4.85; N, 10.37, theoretical value C, 57.68; H, 4.93; N, 10.48 %; 1h NMR (CDCl3,400 MHz), δ H 9.12 (s, 1H); 8.54 (d, 2H); 7.70 (td, 2H); 7.60 (t, 4H); 7.51 (d, 2H); 7.15 (dd, 2H); 5.86 (d, 1H); 3.84 (s, 4H); 3.77 (s, 2H); 2.3 (s, 3H); 1.95 (s, 3H).HR-MS(ESI +,?MeOH):?m/z?calcd?for?[C 26H 26N 4OCoCl] +:?504.11。
Beneficial effect of the present invention is:
Catalyst [(PPMdpa) CoCl of the present invention's design 2] under homogeneous phase condition, chemistry drives the oxidation of catalysis water, under the condition of pH=10, TOF reaches 0.14 s -1, be a kind of without under sensitising agent and electron acceptor condition, there is the catalyst of catalysis water oxidation susceptibility.On the present invention's application earth, the metallic cobalt of rich content, has reduced cost, for future expanding production provide may.For the application of regenerative resource provides new method.
Accompanying drawing explanation
Fig. 1: [(PPMdpa) CoCl of 1 mM 2] cyclic voltammetry curve.A is [(PPMdpa) CoCl 2] in anhydrous acetonitrile; B is [(PPMdpa) CoCl 2] at the phosphate buffer solution of 0.1 mol/L.(working electrode Pt, reference electrode is calomel electrode, is platinum filament to electrode, sweep speed 50mV/s).
Fig. 2: catalyst [(PPMdpa) CoCl 2] (1mM) in the catalysis of the phosphate buffer solution of 0.1mol/L, put oxygen test." ■ " represents to only have cushioning liquid; " zero " represents to comprise 5 mMCe (IV); " ▽ " represents to comprise 5 mmol/LNa 2s 2o 8.
Fig. 3: catalyst [(PPMdpa) CoCl 2] (1mM) in the catalysis of the phosphate buffer solution of 0.1mol/L, put oxygen test."●" represents pH=1; " ■ " represents pH=3; " △ " represents pH=8; " zero " represents pH=10.
The specific embodiment
The present invention's solvent used is all to be analyzed purely, with 5 molecular sieves, remove water treatment, and agents useful for same does not add direct application of specified otherwise and without any specially treated.Ethanol (analyze pure, pilot scale chemical corp, Shanghai); Carrene (analyze pure, pilot scale chemical corp, Shanghai); Ethyl acetate (analyze pure, pilot scale chemical corp, Shanghai); Triethylamine, NaOH (analyze pure, Solution on Chemical Reagents in Shanghai Co., Ltd); 2,4-dimethyl pyrrole, 4-chloromethyl benzoic acid chlorides, two (2-picolyl) are purchased from Sigma company.U.S. Nicolet 20DXB FR-IR type Fourier infrared spectrograph, KBr compressing tablet, 400 ~ 4000cm -1; Japan Shimadzu UV-2450 type UV, visible light spectrophotometer, 800-190 nm; DHG-9140A type electric heating constant temperature drum air-drying box (Shanghai-permanent Science and Technology Ltd.); DZF-6051 type vacuum drying chamber (Shanghai-permanent Science and Technology Ltd.); Shanghai Chen Hua Co., Ltd electrochemical workstation.
Below in conjunction with concrete embodiment, the present invention will be further described, so that those skilled in the art understand the present invention better, but the present invention is not limited to following examples.
embodiment 1:
2,4-dimethyl pyrrole (523.4 mg, 5.25 mmol) and 4-chloromethyl benzoic acid chlorides (997mg, 5.25mmol) be take mol ratio and add CH after 1:1 are mixed 2 cl 2150 mL (concentration of 2,4-dimethyl pyrrole is 35 mmol/L), 40 ℃ of reaction 6h; Then add two (2-picolyl) amine (806 mg, 4.38mmol), triethylamine (442.2 mg, 4.38 mmol), nitrogen protection, 80 ℃ of oil bath backflow 8h; After reaction finishes, use 3 * 30 mL saturated brine extracting and washing, water is used 3 * 30 mL dichloromethane extractions, merges organic phase, and anhydrous sodium sulfate drying, revolves and steam solvent, obtains red oil; Silica gel column chromatography is separated, uses eluent ethyl acetate, obtains the faint yellow sticky solid of 669 mg, is 4-((bis-(pyridine-2-methylene) amino) methyl) (3,5-dimethyl-1H-pyrroles-2-yl) ketone (PPMdpa) productive rate 66%.Then get PPMdpa(197 mg, 0.48 mmol) and CoCl 26H 2o(142 mg, 0.53mmol) take mol ratio and after 1:1.1 mixes, add (concentration of PPMdpa is 9.6 mmol/L) in 50 mL absolute ethyl alcohols, 70 ℃ of reaction 3h; Ether diffusion, filters and vacuum drying, obtains blue solid 238 mg, two (pyridine-2-methylene) amino) methyl) cobalt chloride complex ([(PPMdpa) CoCl of (3,5-dimethyl-1H-pyrroles-2-yl) ketone 2]), productive rate 91%.Its molecular formula is C 26h 26n 4oCoCl 2, elementary analysis measured value C, 57.79; H, 4.85; N, 10.37, theoretical value C, 57.68; H, 4.93; N, 10.48 %; 1h NMR (CDCl 3, 400 MHz), δ h9.12 (s, 1H); 8.54 (d, 2H); 7.70 (td, 2H); 7.60 (t, 4H); 7.51 (d, 2H); 7.15 (dd, 2H); 5.86 (d, 1H); 3.84 (s, 4H); 3.77 (s, 2H); 2.3 (s, 3H); 1.95 (s, 3H).HR-MS(ESI +,?MeOH): ?m/z?calcd?for?[C 26H 26N 4OCoCl] +:?504.11。
embodiment 2:
2,4-dimethyl pyrrole (354.4 mg, 0.38 mmol) and 4-chloromethyl benzoic acid chlorides (36 mg, 0.19 mmol) be take mol ratio and add CH after 2:1 are mixed 2 cl 250 mL (herein 2, the concentration of 4-dimethyl pyrrole is 7.6 mmol/L), 40 ℃ of reaction 2h; Then add two (2-picolyl) amine (35 mg, 0.19 mmol), triethylamine (638 mg, 0.76mmol), nitrogen protection, 80 ℃ of oil bath backflow 8h; After reaction finishes, use 3 * 30 mL saturated brine extracting and washing, water is used 3 * 30 mL dichloromethane extractions, merges organic phase, and anhydrous sodium sulfate drying, revolves and steam solvent, obtains red oil; Silica gel column chromatography is separated, uses eluent ethyl acetate, obtains faint yellow sticky solid 4-((bis-(pyridine-2-methylene) amino) methyl) (3,5-dimethyl-1H-pyrroles-2-yl) ketone (PPMdpa), productive rate 29%.Then get PPMdpa(197 mg, 0.48 mmol) and CoCl 26H 2o(142 mg, 0.53mmol) take mol ratio and after 1:1.1 mixes, add (concentration of PPMdpa is 24 mmol/L) in 20 mL absolute ethyl alcohols, 70 ℃ of reaction 1h; Ether diffusion, filters and vacuum drying, obtains blue solid 189 mg, two (pyridine-2-methylene) amino) methyl) cobalt chloride complex ([(PPMdpa) CoCl of (3,5-dimethyl-1H-pyrroles-2-yl) ketone 2]), productive rate 73%.
embodiment 3:
2,4-dimethyl pyrrole (354.4 mg, 0.38 mmol) and 4-chloromethyl benzoic acid chlorides (144 mg, 0.76mmol) be take mol ratio and add CH after 1:2 are mixed 2cl 2200 mL(herein 2, and the concentration of 4-dimethyl pyrrole is 1.9 mmol/L), 40 ℃ of reaction 10 h; Then add two (2-picolyl) amine (140 mg, 0.76mmol), triethylamine (159 mg, 0.19mmol), nitrogen protection, 80 ℃ of oil bath backflow 8h; After reaction finishes, use 3 * 30 mL saturated brine extracting and washing, water is used 3 * 30 mL dichloromethane extractions, merges organic phase, and anhydrous sodium sulfate drying, revolves and steam solvent, obtains red oil; Silica gel column chromatography is separated, uses eluent ethyl acetate, obtains faint yellow sticky solid 4-((bis-(pyridine-2-methylene) amino) methyl) (3,5-dimethyl-1H-pyrroles-2-yl) ketone (PPMdpa), productive rate 35%.Then get PPMdpa(197 mg, 0.48 mmol) and CoCl 26H 2o(257 mg, 0.96 mmol) take mol ratio adds (concentration of PPMdpa is 4.8 mmol/L) in 100 mL absolute ethyl alcohols herein, 70 ℃ of reaction 6h after 1:2 mixes; Ether diffusion, filters and vacuum drying, obtains blue solid 220 mg, two (pyridine-2-methylene) amino) methyl) cobalt chloride complex ([(PPMdpa) CoCl of (3,5-dimethyl-1H-pyrroles-2-yl) ketone 2]), productive rate 85%.
embodiment 4:
2,4-dimethyl pyrrole (354.4 mg, 0.38mmol) and 4-chloromethyl benzoic acid chlorides (48 mg, 0.25mmol) be take mol ratio and add CH after 1.5:1 are mixed 2cl 2100 mL (concentration of 2,4-dimethyl pyrrole is 3.8 mmol/L), 40 ℃ of reaction 4h; Then add two (2-picolyl) amine (105 mg, 0.57mmol), triethylamine (957 mg, 1.14mmol), nitrogen protection, 80 ℃ of oil bath backflow 16h; After reaction finishes, use 3 * 30 mL saturated brine extracting and washing, water is used 3 * 30 mL dichloromethane extractions, merges organic phase, and anhydrous sodium sulfate drying, revolves and steam solvent, obtains red oil; Silica gel column chromatography is separated, uses eluent ethyl acetate, obtains faint yellow sticky solid 4-((bis-(pyridine-2-methylene) amino) methyl) (3,5-dimethyl-1H-pyrroles-2-yl) ketone (PPMdpa), productive rate 52%.Then get PPMdpa(197 mg, 0.48 mmol) and CoCl 26H 2o(64mg, 0.24mmol) take mol ratio and after 2:1 mixes, add (concentration of PPMdpa is 6.8 mmol/L) in 70 mL absolute ethyl alcohols, 70 ℃ of reaction 6h; Ether diffusion, filters and vacuum drying, obtains blue solid 102 mg, two (pyridine-2-methylene) amino) methyl) cobalt chloride complex ([(PPMdpa) CoCl of (3,5-dimethyl-1H-pyrroles-2-yl) ketone 2]), productive rate 79%.
embodiment 5:
2,4-dimethyl pyrrole (354.4 mg, 0.38mmol) and 4-chloromethyl benzoic acid chlorides (107 mg, 0.715 mmol) be take mol ratio and add CH after 1:1.5 are mixed 2 cl 2120 mL(2, the concentration of 4-dimethyl pyrrole is 3.16 mmol/L),, 40 ℃ of reaction 4h; Then add two (2-picolyl) amine (62 mg, 0.38 mmol), triethylamine (159 mg, 0.19mmol), nitrogen protection, 80 ℃ of oil bath backflow 4h; After reaction finishes, use 3 * 30 mL saturated brine extracting and washing, water is used 3 * 30 mL dichloromethane extractions, merges organic phase, and anhydrous sodium sulfate drying, revolves and steam solvent, obtains red oil; Silica gel column chromatography is separated, uses eluent ethyl acetate, obtains faint yellow sticky solid 4-((bis-(pyridine-2-methylene) amino) methyl) (3,5-dimethyl-1H-pyrroles-2-yl) ketone (PPMdpa), productive rate 52%.Then get PPMdpa(197 mg, 0.48 mmol) and CoCl 26H 2o(192mg, 0.72mmol) take mol ratio and after 1:1.5 mixes, add (concentration of PPMdpa is 9.6 mmol/L) in 50 mL absolute ethyl alcohols, 70 ℃ of reaction 4h; Ether diffusion, filters and vacuum drying, obtains blue solid 226 mg, two (pyridine-2-methylene) amino) methyl) cobalt chloride complex ([(PPMdpa) CoCl of (3,5-dimethyl-1H-pyrroles-2-yl) ketone 2]), productive rate 87%.
embodiment 6:
2,4-dimethyl pyrrole (354.4 mg, 0.38mmol) and 4-chloromethyl benzoic acid chlorides (71.8 mg, 0.38mmol) be take mol ratio and add CH after 1:1 are mixed 2cl 2100 mL(2, the concentration of 4-dimethyl pyrrole is 3.8 mmol/L), 40 ℃ of reaction 4h; Then add two (2-picolyl) amine (81 mg, 0.5 mmol), triethylamine (756 mg, 0.90 mmol), nitrogen protection, 80 ℃ of oil bath backflow 4h; After reaction finishes, use 3 * 30 mL saturated brine extracting and washing, water is used 3 * 30 mL dichloromethane extractions, merges organic phase, and anhydrous sodium sulfate drying, revolves and steam solvent, obtains red oil; Silica gel column chromatography is separated, uses eluent ethyl acetate, obtains faint yellow sticky solid 4-((bis-(pyridine-2-methylene) amino) methyl) (3,5-dimethyl-1H-pyrroles-2-yl) ketone (PPMdpa), productive rate 60%.Then get PPMdpa(197 mg, 0.48 mmol) and CoCl 26H 2o(142 mg, 0.53mmol) take mol ratio and after 1:1.1 mixes, add (concentration of PPMdpa is 13.2 mmol/L) in 40 mL absolute ethyl alcohols, 70 ℃ of reaction 5h; Ether diffusion, filters and vacuum drying, obtains blue solid 238 mg, two (pyridine-2-methylene) amino) methyl) cobalt chloride complex ([(PPMdpa) CoCl of (3,5-dimethyl-1H-pyrroles-2-yl) ketone 2]), productive rate 89%.
[(PPMdpa) CoCl 2] the data of cyclic voltammetry show complex [(PPMdpa) CoCl 2] to have very low overvoltage (η=0.6 V) current density be 1.6 mAcm -2(accompanying drawing 1).This illustrates [(PPMdpa) CoCl 2] as the catalyst of water oxidation, be feasible.
With complex [(PPMdpa) CoCl 2] as the visible accompanying drawing 2 of oxygen release graphics of the catalyst of water oxidation.Experimental result shows catalyst [(PPMdpa) CoCl 2] there is no electron acceptor Ce (IV) or S 2o 8 2-existence condition under also can flower forcing water releasing oxygen, show that catalyst itself can be used as electron acceptor.
In order to explore best catalytic condition, we change the pH of cushioning liquid, the visible accompanying drawing 3 of experimental result.As can be seen from the figure under the condition of pH=10, the condition of catalysis water oxidation is best, and TON is that 14.9, TOF is 0.14 s -1, this is that the first chemistry not using electron acceptor drives catalysis water oxidation system.

Claims (9)

1. a unimolecule catalyst for catalysis water oxidation, is characterized in that, described unimolecule catalyst is a kind of list
Core cobalt complex, its name is called 4-((bis-(pyridine-2-methylene) amino) methyl) the cobalt chloride complex of (3,5-dimethyl-1H-pyrroles-2-yl) ketone, referred to as [(PPMdpa) CoCl 2], structural formula is:
Figure 2013106990176100001DEST_PATH_IMAGE001
.
2. a preparation method for the unimolecule catalyst of catalysis water oxidation, is characterized in that, according to following steps, carries out:
(1) after being mixed with 4-chloromethyl benzoic acid chlorides, 2,4-dimethyl pyrrole adds carrene reaction;
(2) in mixed system, add successively two (2-picolyl) amine and triethylamine, under nitrogen protection, oil bath refluxes;
(3) reaction finishes the rear saturated brine extracting and washing of using, and water is used dichloromethane extraction, merges organic phase, and anhydrous sodium sulfate drying, revolves and steam solvent, obtains red oil;
(4) red oil is separated through silica gel column chromatography, with eluent ethyl acetate, obtain light yellow viscous liquid, be 4-((bis-(pyridine-2-methylene) amino) methyl) (3,5-dimethyl-1H-pyrroles-2-yl) ketone, be abbreviated as PPMdpa;
(5) after being mixed with cobalt chloride, PPMdpa adds absolute ethyl alcohol reaction, ether diffusion, filter, obtain blue solid, be 4-((bis-(pyridine-2-methylene) amino) methyl) (3,5-dimethyl-1H-pyrroles-2-yl) the cobalt chloride complex of ketone, is called for short [(PPMdpa) CoCl 2].
3. the preparation method of the unimolecule catalyst that a kind of catalysis water according to claim 2 is oxidized, it is characterized in that, described in step (1) 2, the mol ratio of 4-dimethyl pyrrole and 4-chloromethyl benzoic acid chlorides is 1:2～2:1, wherein 2, the concentration of 4-dimethyl pyrrole in mixed solution is 1.9-35 mmol/L; Described reaction is 40 ℃ of reaction 2～10h.
4. the preparation method of the unimolecule catalyst of a kind of catalysis water oxidation according to claim 2, is characterized in that, two (2-picolyl) amine described in step (2) and the mol ratio of 2,4-dimethyl pyrrole are 1:2～2:1; The mol ratio of triethylamine and two (2-picolyl) amine is 4:1～1:4; It is 80 ℃ of 4～16h that reflux that described oil bath refluxes.
5. the preparation method of the unimolecule catalyst of a kind of catalysis water oxidation according to claim 2, is characterized in that, the mol ratio of the PPMdpa described in step (5) and cobalt chloride is 1:2～2:1; Wherein the concentration of PPMdpa in mixed liquor is 4.8～24 mmol/L; Described reaction is 70 ℃ of reaction 1～6h.
6. the preparation method of the unimolecule catalyst of a kind of catalysis water oxidation according to claim 3, is characterized in that, described 2, and the mol ratio of 4-dimethyl pyrrole and 4-chloromethyl benzoic acid chlorides is 1:1, adds CH 2cl 2150 mL, 40 ℃ of reaction 6h.
7. the preparation method of the unimolecule catalyst that a kind of catalysis water according to claim 4 is oxidized, it is characterized in that, described two (2-picolyl) amine and 2,4-dimethyl pyrrole mol ratio is 1:1.2, the mol ratio of described triethylamine and two (2-picolyl) amine is 1:1,80 ℃ of oil bath backflow 8h.
8. the preparation method of the unimolecule catalyst of a kind of catalysis water oxidation according to claim 5, is characterized in that, described PPMdpa and cobalt chloride mol ratio are 1:1.1, add absolute ethyl alcohol 50 mL, 70 ℃ of reaction 3h.
9. the preparation method of the unimolecule catalyst of a kind of catalysis water oxidation according to claim 2, is characterized in that, prepared unimolecule catalyst is applied to the oxidation of catalysis water and discharges oxygen.
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