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  • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
  • B01J2531/0202—Polynuclearity
  • B01J2531/0205—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J2531/0213—Complexes without C-metal linkages
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
  • B01J2531/23—Calcium
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
  • B01J2531/72—Manganese
• • 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

Definitions

• This invention relates to a novel class of biomimetic water cracking catalysts.
• the present invention relates to a water cracking catalyst containing a [M n4 Ca0 4 ] core structure, a process for its preparation and its use.
• Such compounds can be used as artificial catalysts for catalytic water cracking.
• the photosystem II of photosynthetic organisms is the only biological system in nature that can efficiently and safely utilize cheap metal ions (Mn, Ca) to achieve water cracking, obtain electrons, protons, and release oxygen.
• Mn, Ca metal ions
• the reason why Photosystem II can efficiently and safely crack water is that it has a unique Mn 4 Ca cluster biohydrogen catalyst.
• the core of the bio-hydrolysis catalyst consists of a Mn 3 Ca0 4 cuba and a Mn ion connected through a ⁇ 2 ⁇ bridge to form an asymmetric [Mn 4 CaO ] (
• the value of n depends on the redox state of the catalyst, which may be 4 or 5) a heteronuclear metal cluster having a ligand provided by six carboxyl groups, one imidazole and four water molecules in the periphery.
• the biocatalyst undergoes 5 different states (S 0 , Si, S 2 , S 3 , S 4 ).
• the Water Cracking Biocatalytic Center in Photosystem II provides an ideal blueprint for a 401*, high efficiency, environmentally friendly, artificial water cracking catalyst. How to chemically synthesize and prepare a bio-cracking catalytic center is an important scientific frontier and a very challenging scientific problem. There have been no successful cases.
• the present invention provides a novel method: using a low-cost metal ion (M n 2+ , Ca 2+ ion), simple acid-reducing and Mn0 4 as a starting material, two-step synthesis containing [Mn 3 Ca0 4 ] cube
• the alkane and a Mn ion are bridged through a ⁇ 2 ⁇ to form an asymmetric [Mn 4 Ca0 4 ] core structure, and the peripheral ligand of [Mn 4 Ca0 4 ] consists of eight carboxyl anions and three exchangeable neutrals.
• the composition of the four manganese ions is +3, +3, +4, +4.
• These compounds are structurally very similar to the biohydrolysis catalytic center, and we found that these compounds have biological water Similar physicochemical properties of the cracking catalytic center. In the presence of an oxidizing agent, these compounds catalyze the cracking of water, release oxygen, and transfer electrons released by water splitting to the surface of the electrode to form an electric current.
• the structurally modified derivative can be used as an artificial catalyst for water cracking.
• the invention adopts simple Mn +2 , Ca 2+ inorganic compound and simple organic carboxylic acid, and uses a permanganate anion as an oxidant to synthesize a water cracking catalyst containing a [Mn 4 C a 0 4 ] asymmetric cluster compound in two steps.
• These new catalysts catalyze the cracking of water in the presence of oxidants, releasing oxygen. They also catalyze water cracking on the electrode surface, releasing electrons to the electrode surface to form an electric current.
• the object of the present invention is to synthesize a preparation method and application of a series of water-cracking catalysts containing a [Mn 4 Ca0 4 ] core structure.
• the peripheral ligand of the [Mn 4 Ca0 4 ] cluster is provided by eight carboxylate anions (RiCC ) and three neutral ligands (1 ⁇ , L 2 , L 3 ).
• the valence states of the four Mn ions are +3, +3, +4, +4, respectively, and the entire cluster is electrically neutral.
• Ri is selected from H or d. 8 ⁇ M ⁇ J ;
• L 1 ⁇ L 2 , L 3 three ligands are the same or different, each independently selected from the group consisting of a carboxylic acid molecule and a derivative thereof, pyridine, imidazole, pyrazine, quinine, isoquinoline and derivatives thereof, or A small, neutral molecule that can be exchanged for water molecules, alcohol molecules, ketones, nitriles (such as acetonitrile), and esters.
• the carboxylic acid anion may be a carboxylic acid anion such as citric acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid or caproic acid.
• it may be hydrogen (H), methyl (CH 3 ), ethyl (C 2 H 5 ), n-propyl (CH 2 CH 2 CH 3 ), isopropyl (CH(CH 3 ) 2 ), or Butyl (-(CH 2 ) 3 CH 3 ), isobutyl (CH(CH 3 )C 2 H 5 ), tert-butyl (-C(CH 3 ) 3 ), n-(CH 2 ) 4 CH 3 ), iso (-CH(CH 3 )C 3 H 8 ), and the like.
• the compound of formula I is selected from the group consisting of
• Equation 1-3 A method for producing a compound of the formula [MmCaO KRiCO ⁇ O ⁇ XI ⁇ XLs), which is represented by the formula I, characterized in that the method comprises:
• the acid preferably organic carboxylic acid
• oxidizing agent Mn 2+ and Ca 2+ salt
• the reaction is heated in an acetonitrile solution for 10 to 60 minutes to obtain a ochre solution, and the precipitate is removed; the solution is at o. c crystallizes to give brown crystals;
• Step 2 The brown crystal obtained in the first step is dissolved in an ester solvent, and the organic ligand L 2 and L 3 are added to obtain a final product.
• the divalent manganese salt Mn 2+ can be a variety of Mn 2+ -containing carboxylates.
• the carboxylic acid anion (RiCC) is as described above, and may be, for example, a carboxyl group such as formate, acetate, propionate, butyrate, isobutyrate, valerate, isovalerate, pivalate or hexanoate. And a derivative thereof (preferably acetate, pivalate); or a divalent manganese salt such as Mn(C10 4 ) 2 , MnS0 4 , Mn(N0 3 ) 2 or Mn(CF 3 S0 3 ) 2 .
• the Ca 2+ salt can be a variety of carboxylates.
• the carboxylic acid anion (RiCC) is as described above, and may be, for example, a carboxyl group such as citrate, acetate, propionate, butyrate, isobutyrate, valerate, isovalerate, pivalate or hexanoate. And a derivative thereof (preferably acetate, pivalate); or a calcium salt such as Ca(C10 4 ) 2 , Ca(N0 3 ) 2 or Ca(CF 3 S0 3 ) 2 .
• the oxidizing agent is preferably a permanganate anionic oxidizing agent, more preferably tetrabutylammonium permanganate ((C 4 H 9 ) 4 NMn0 4 ).
• the acid is preferably an organic carboxylic acid.
• carboxyl groups such as capric acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, caproic acid and derivatives thereof (preferably acetic acid, pivalic acid).
• the volume of the acetonitrile solvent in the next step is about 60-100 ml per mM of the calcium salt with acetonitrile. This reaction can only be carried out in an acetonitrile solvent, and the target compound cannot be obtained in an alcohol or other organic solvent.
• the ester organic solvent in the second step of recrystallization may be an ester such as ethyl acetate, methyl acetate or propyl propionate.
• the organic ligands are the same or different, each independently ilk ⁇ from the carboxylic acid molecule and its derivatives, pyridine, imidazole, pyrazine, quinine and their derivatives, or water molecules, alcohol molecules, ketones, nitriles (such as acetonitrile), esters and other neutral small molecules that can be exchanged.
• the temperature should be 60. C ⁇ 90. C.
• the reaction time can be from 10 to 60 minutes.
• the invention also provides the use of a compound of formula I as a water cracking catalyst.
• the compound of the formula I of the present invention is used to drive catalytic cracking of water at the surface of the electrode, or in the presence of an oxidant (which may be a stable oxidant or a photo-induced transient oxidant), releasing oxygen, Protons and electrons.
• an oxidant which may be a stable oxidant or a photo-induced transient oxidant
• the present invention also provides a water-cracking catalyst comprising the above-mentioned [MmCaC ⁇ KRiCO ⁇ O ⁇ XI ⁇ XLs) compound of the present invention.
• the crystal structure is shown in Fig. 1, and the single crystal parameters are shown in Table 1. Table 1: Single crystal parameters of compound 1
• the crystal structure is shown in Fig. 3.
• the single crystal parameters are shown in Table 3: Table 3: Single of compound 3 Crystal parameter
• the present invention now utilizes a simple Mn +2 , Ca 2+ inorganic compound and a simple carboxylic acid, a permanganate anion as an oxidant, and a two-step synthesis to obtain a core containing a [Mn 4 Ca 0 4 ] asymmetric cluster. Catalyze the cracking of water in the presence of an electric or oxidant and release oxygen, electrons and protons.
• the neutral [MmCaO ⁇ RiCO ⁇ I ⁇ I ⁇ Ls cluster obtained by the invention can be used as a water cracking catalyst for the surface of the electrode, or has an oxidant (can be an oxidant of the spike, or a light-induced transient)
• the oxidant drives the catalytic cracking of water, releasing oxygen, protons and electrons.
• Such novel [Mn 4 C a 0 4 ] catalysts have not been reported in the literature.
• Figure 1 is a view showing the crystal structure of Compound 1 prepared in Example 1 of the present invention. For clarity, the sulfhydryl and solvent molecules of the sub and tert-butyl groups are omitted.
• Figure 2 is a view showing the crystal structure of Compound 2 prepared in Example 2 of the present invention. For clarity, the methyl and solvent molecules of the sub and tert-butyl groups are omitted.
• Fig. 3 is a view showing the crystal structure of the compound 3 prepared in Example 3 of the present invention.
• the methyl group and the solvent molecule of the sub- and tert-butyl groups are omitted.
• Figure 4 is a graph showing the variation of the UV-visible absorption light of the corresponding compound 1 with water in Example 4 of the present invention.
• Fig. 5 is a view showing the fifth embodiment of the present invention, which corresponds to the electrochemical data of the catalytic release of the compound 1 itself and its catalytic water on the electric converging surface to release electrons.
• FIG. 6 is a sixth embodiment of the present invention, showing an electron paramagnetic signal obtained by oxidizing compound 1, which supports the valence states of four Mil ions in ground state compound 1 being +3, +3, +4, respectively. +4 price.
• Figure 7 is a seventh embodiment of the present invention which is a measurement of the liberation of oxygen by the catalyzed water cleavage of Compound 1 in the presence of an oxidizing agent.
• Example 1 Compound 1 [Mn 4 Ca0 4 ](C 5 H 9 0 2 ) 8 (C 5 H 9 0 2 H) 2 (C 5 H 5 N)
• the preparation method is as follows:
• the first step is the synthesis of the compound 1 precursor: adding tetrabutyl permanganate to a 100 ml round bottom flask
• the second step is recrystallization.
• the crystals obtained in the first step were collected, dissolved in ethyl acetate, and recrystallized by adding 2% pyridine (volume ratio). After 1 to 2 weeks, brown crystals were precipitated, washed with cyclohexane, dried in vacuo, and the yield was ⁇ 40. % (based on the number of moles of Ca ions).
• the structural formula of the compound 1 is [Mn 4 Ca0 4 ](C 5 H 9 0 2 ) 8 (C 5 H 9 0 2 H) 2 (C 5 H 5 N)*C 6 H 12 (Note: cyclohexane is a solvent Molecular formula: Molecular formula: C HKwNOwCaMn ⁇ Elemental analysis theoretical value: C, 48.83; H, 7.32; N, 0.93. Experimental value: C, 49.14; H, 7.59; N, 1.18.
• the structural formula of the compound 2 is [MmCaO KCsHgC ⁇ CsHgC ⁇ HWCsHsN .
• Molecular formula C 55 H 92 N 2 0 22 CaMn 4 .
• the chemical structure of the compound 2 is as shown in the following formula 1-2, and the single crystal measurement thereof is shown in Table 2.
• the crystal space structure is shown in Fig. 2.
• One step is the synthesis of the compound precursor: To a 100 ml round bottom flask was added tetrabutylammonium permanganate (Bu n 4 NMn0 4 , 4 mmol), acetic acid argon ( Mn(CH 3 C0 2 ) 2 , 1 mmol ), calcium acetate (Ca(CH 3 C0 2 ) 2 , 1 mmol) and pivalic acid ((CH 3 ) 3 CC0 2 H, 40 mmol) at 80. After continuous reaction in C acetonitrile for 25 min, the mixture was stopped and filtered to remove a small amount of precipitate. The obtained brown mother liquor was placed at 0 ° C for 1 to 2 weeks to precipitate brown crystals.
• tetrabutylammonium permanganate Bu n 4 NMn0 4 , 4 mmol
• acetic acid argon Mn(CH 3 C0 2 ) 2 , 1 mmol
• calcium acetate Ca(
• the second step is recrystallization: The crystals obtained in one step are collected, dissolved in ethyl acetate, and recrystallized by adding 1% isoquinoline (volume ratio). After 1 to 2 weeks, black crystals are collected and rinsed with cyclohexane. Dry in vacuo, yield ⁇ 40% (depending on the moles of Ca ions).
• the structural formula of the compound 3 is [Mn 4 Ca0 4 ](C 5 H 9 0 2 ) 9 (C 5 H 9 0 2 H) 2 (C 9 H 7 N), and the molecular formula: C 59 H 99 N0 24 CaMn 4 .
• the chemical structure of the compound 3 is as shown in the following formula 1-3, and the specific single crystal is determined by the reference of L ⁇ 3, and the crystal space structure thereof is shown in Fig. 3.
• Electrochemical determination of Compound 1 and its catalytic water cleavage on the electrode surface The electrochemical of the compound 1 and its catalytic water cleavage on the electrode surface were tracked using an electrochemical workstation.
• the working electrode is a glassy carbon electrode
• the counter electrode is a platinum electrode
• silver/nitric acid silver (10 mM) is a reference electrode.
• the electrolyte was acetonitrile and the electrolyte was tetrabutylhexammine (C 4 H 9 ) 4 NPF 6 ), which was scanned for >3 ⁇ 4 lOOmV/s.
• the inset of Figure 6 is the cyclic voltammetry of Compound 1 in the absence of water.
• the oxygen evolution activity of the catalytic water decomposition was measured on a Clark-type oxygen electrode (Fig. 7).
• aqueous solution containing the oxidizing agent t-butyl hydroperoxide, 0.7 M
• a rapid release of oxygen was observed by adding 125 ⁇ of Compound 1, while no oxygen was observed when the reference compound (Mn(C10 4 ) 2 ) was added.
• the arrow in the figure shows the loading position.
• Figure 7 illustrates that Compound 1 has catalytic activity for catalyzing aqueous cleavage to release oxygen.

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