CN115710292A - Bionic water cracking catalyst containing rare earth ions and preparation method and application thereof - Google Patents

Bionic water cracking catalyst containing rare earth ions and preparation method and application thereof Download PDF

Info

Publication number
CN115710292A
CN115710292A CN202110970907.0A CN202110970907A CN115710292A CN 115710292 A CN115710292 A CN 115710292A CN 202110970907 A CN202110970907 A CN 202110970907A CN 115710292 A CN115710292 A CN 115710292A
Authority
CN
China
Prior art keywords
cluster
formula
single crystal
rare earth
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202110970907.0A
Other languages
Chinese (zh)
Inventor
张纯喜
李彦洗
姚若青
陈长辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Chemistry CAS
Original Assignee
Institute of Chemistry CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Chemistry CAS filed Critical Institute of Chemistry CAS
Priority to CN202110970907.0A priority Critical patent/CN115710292A/en
Publication of CN115710292A publication Critical patent/CN115710292A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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

Abstract

The invention discloses a bionic water cracking catalyst containing rare earth ions, a preparation method and application thereof, wherein the catalyst contains [ Mn n XO m ]A cluster compound, wherein n is 3 or 4; m is 2,4 or 5, the cluster compound is a rare earth manganese heteronuclear metal cluster compound which contains rare earth ions X and one of the following core structures: [ Mn ] 3 XO 2 ]Heteronuclear metal cluster skeleton core, [ Mn ] 4 XO 4 ]Heteronuclear metal cluster framework core and [ Mn ] 4 XO 5 ]A heteronuclear metal cluster skeletal core, said X being selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium. The valence of the manganese ions of the cluster compounds in the invention is +3 or +4, and the cluster compounds have important value in the aspect of magnetic materials. Further, [ Mn ] obtained by the present invention 4 XO 4 ]And [ Mn 4 XO 5 ]The cluster compound can be used as an artificial water cracking catalyst for catalytic cracking of water on the surface of an electrode or driven by an oxidant (which can be a stable oxidant or a transient oxidant generated by light induction).

Description

Bionic water cracking catalyst containing rare earth ions and preparation method and application thereof
Technical Field
The invention relates to a bionic water cracking catalyst containing rare earth ions, a preparation method and application thereof, belonging to the technical field of catalysts.
Background
The problems of energy crisis and environmental pollution are two key problems restricting the continuous development of human society in the twenty-first century. If abundant water on the earth can be cracked by using inexhaustible solar energy, oxygen is released, electrons and protons are obtained, and electric energy or hydrogen energy is generated, the problems of energy crisis and environmental pollution of human beings can be fundamentally solved. However, water is a thermodynamically very stable substance and a suitable catalyst is necessary to achieve its efficient and safe cracking. Recently, researchers in the prior art use noble metals such as ruthenium, iridium and the like and some complex ligands to synthesize artificial catalysts with water cracking function, but the use of noble metals and complex ligands leads to high preparation cost of the catalysts and easy environmental pollution, so that the catalysts are difficult to popularize and apply. How to prepare the water cracking catalyst with high efficiency, stability, low price and environmental protection is an unsolved scientific problem.
The photosystem II of the photosynthetic organisms is the only biological system which can efficiently and safely utilize cheap metal ions to realize water splitting, obtain electrons and protons and release oxygen in the nature. Photosystem II is capable of efficiently and safely splitting water because it possesses a unique [ Mn ] 4 CaO 5 ]The heteronuclear metal cluster biocatalyst has six carboxyl groups, one imidazole ring and four water molecules as ligands around its periphery. During the water splitting process, the biocatalyst undergoes five different states (S) 0 ,S 1 ,S 2 ,S 3 ,S 4 ) (ii) a Wherein S is 1 The state is a dark steady state, and the valence states of the four manganese ions correspond to (+ 3, +3, +4, + 4). The disclosure of the water cracking catalysis center structure of the photosynthetic organisms provides an ideal blueprint for developing the efficient, stable, cheap and environment-friendly bionic water cracking catalyst.
How to chemically synthesize the catalytic center similar to biological water cracking is an important scientific frontier and is also an extremely challenging scientific problem. Patent ZL201510065238.7 discloses a catalyst containing [ Mn 4 CaO 4 ]A core structured water cracking catalyst, a method for preparing the same and use thereof; patent ZL201711059799.1 discloses a catalyst containing [ Mn 3 SrO 4 ]And [ Mn 4 SrO 4 ]A cluster compound with a core structure, a preparation method and application thereof. These two patents protect the structural formulae shown below, respectively:
Figure BDA0003225650070000011
in the formulae 1 and 2, R 1 Is selected from H or C 1-8 A linear or branched alkyl group; l is 1 、L 2 、L 3 、L 4 The ligand is four same or different ligands, and is independently selected from carboxylic acid molecules and derivatives thereof, pyridine, imidazole, pyrazine, quinoline, isoquinoline and derivatives thereof, or exchangeable small molecules such as water molecules, alcohol molecules, ketones, nitriles (such as acetonitrile), esters and the like.
Synthesis of the above two alkaline earth metal ions [ Mn 4 CaO 4 ]And [ Mn 4 SrO 4 ]The cluster is the bionic cluster which is most similar to a biological water splitting catalytic center so far, but the stability of the bionic cluster needs to be further improved.
Disclosure of Invention
In order to improve the above technical problems, the present invention introduces a rare earth ion X (e.g., at least one selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium) into a synthesis catalyst, providing a three-kind core structure of [ Mn 3 XO 2 ]、[Mn 4 XO 4 ]And [ Mn 4 XO 5 ]The rare earth manganese heteronuclear metal cluster compound and the preparation method and the application thereof.
The invention is realized by the following technical scheme:
a rare earth manganese heteronuclear metal cluster compound having [ Mn n XO m ]A heteronuclear metal cluster framework core, wherein n is 3 or 4; m is 2,4 or 5; x is selected from rare earth elements.
According to an embodiment of the invention, the rare earth heteronuclear metal cluster has one of the following core structures: [ Mn ] 3 XO 2 ]Heteronuclear metal cluster skeleton core, [ Mn ] 4 XO 4 ]Heteronuclear metal cluster framework core and [ Mn ] 4 XO 5 ]The heteronuclear metal cluster skeleton core, and X is selected from rare earth elements.
According to the invention, said X is selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium.
According to one embodiment of the invention, the cluster compound has the formula Mn 3 XO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 Has a structure shown as formula I, and contains one rare earth ion X and three Mn ions which pass through 2 mu 3 Connecting by O bridges to [ Mn 3 XO 2 ]Heteronuclear metal cluster framework cores;
[Mn 3 XO 2 ]the peripheral ligand of the heteronuclear metal cluster skeleton core is composed of nine carboxylate anions R 1 CO 2 - And three neutral carboxylic acid ligands R 1 CO 2 H, wherein the valence states of three Mn ions are +3, +3, +4, respectively, and the whole cluster compound is electrically neutral;
Figure BDA0003225650070000021
wherein X is selected from Sc, Y, la, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb or Lu;
R 1 is the same as orDifferent, independently of one another, from H or C 1-8 Straight or branched chain alkyl.
According to the invention, the carboxylate anion R 1 CO 2 - May be at least one of formate, acetate, propionate, isopropionate, butyrate, isobutyrate, tertbutyrate, valerate, isovalerate, pivalate, hexanoate, and the like. Namely, R 1 Can be hydrogen (H) or methyl (-CH) 3 ) Ethyl (-C) 2 H 5 ) N-propyl (-CH) 2 CH 2 CH 3 ) Isopropyl (-CH (CH) 3 ) 2 ) N-butyl (- (CH) 2 ) 3 CH 3 ) Isobutyl (-CH (CH) 3 )C 2 H 5 ) T-butyl (-C) (CH) 3 ) 3 ) N-pentyl (- (CH) 2 ) 4 CH 3 ) Isopentyl (-CH) 2 CH 2 CH(CH 3 ) 2 ) Tert-amyl (-CH) 2 C(CH 3 ) 3 ) Or n-hexyl (- (CH) 2 ) 5 CH 3 ) And the like.
According to the invention, R 1 CO 2 H may be at least one of formic acid, acetic acid, propionic acid, isopropanoic acid, butyric acid, isobutyric acid, t-butyric acid, valeric acid, isovaleric acid, pivalic acid, caproic acid, and the like.
Preferably, the cluster compound having the structure shown in formula I is selected from any one of the following cluster compounds 1 to 5:
cluster compound 1 of the formula Mn 3 YO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 Wherein R is 1 = tert-butyl group.
Preferably, cluster 1 is a single crystal; the structure is shown as formula I-1:
Figure BDA0003225650070000022
the single crystal belongs to a triclinic system, the space group is P-1, and the unit cell parameter is
Figure BDA0003225650070000023
Figure BDA0003225650070000024
α =77.526 (3) °, β =87.004 (2) °, γ =65.818 (3) °, Z =2, and has a volume of
Figure BDA0003225650070000025
Cluster 2 of the formula Mn 3 LaO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 Wherein R is 1 = tert-butyl group.
Preferably, cluster 2 is a single crystal; the structure is shown as formula I-2:
Figure BDA0003225650070000031
the single crystal belongs to a monoclinic system, and the space group is P2 1 N, unit cell parameter of
Figure BDA0003225650070000032
Figure BDA0003225650070000033
α =90 °, β =107.516 (4) °, γ =90 °, Z =4, and volume
Figure BDA0003225650070000034
Cluster 3 of the formula Mn 3 GdO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 Wherein R is 1 = tert-butyl group.
Preferably, cluster 3 is a single crystal; the structure is shown as formula I-3:
Figure BDA0003225650070000035
the single crystal belongs to a triclinic system, the space group is P-1, and the unit cell parameter is
Figure BDA0003225650070000036
Figure BDA0003225650070000037
α =77.898 (2) °, β =87.087 (2) °, γ =65.755 (2) °, Z =2, and has a volume of
Figure BDA0003225650070000038
Cluster compound 4 of the formula Mn 3 DyO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 Wherein R is 1 = tert-butyl group.
Preferably, cluster 4 is a single crystal; the structure is shown as formula I-4:
Figure BDA0003225650070000039
the single crystal belongs to a triclinic system, the space group is P-1, and the unit cell parameter is
Figure BDA00032256500700000310
Figure BDA00032256500700000311
α =77.790 (2) °, β =86.995 (2) °, γ =65.678 (2) °, Z =2, and has a volume of
Figure BDA00032256500700000312
Cluster 5 of the formula Mn 3 LuO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 Wherein R is 1 = tert-butyl group.
Preferably, cluster 5 is a single crystal; the structure is shown as formula I-5:
Figure BDA00032256500700000313
the single crystal belongs to a triclinic system, the space group is P-1, and the unit cell parameter is
Figure BDA00032256500700000314
Figure BDA00032256500700000315
α =77.450 (3) °, β =87.291 (3) °, γ =65.954 (3) °, Z =2, and has a volume of
Figure BDA00032256500700000316
According to one embodiment of the invention, the cluster compound has the formula Mn 4 XO 4 (R 1 CO 2 ) 8 (L 1 )(L 2 )(L 3 ) Has a structure shown as a formula II and contains four Mn ions and one rare earth ion X which are connected into [ Mn ] through four mu-O bridges 4 XO 4 ]Heteronuclear metal cluster framework cores;
[Mn 4 XO 4 ]the peripheral ligand of the heteronuclear metal cluster skeleton core is formed by eight carboxylate anions R 1 CO 2 - And three ligands L 1 、L 2 And L 3 Providing; wherein the valence states of the four Mn ions are +3, +3, +4, +4 respectively.
Figure BDA0003225650070000041
In formula II, rare earth ions X, R 1 Has the meaning as above;
L 1 、L 2 the same or different, each independently selected from carboxylic acid molecule and its derivatives, pyridine, imidazole, pyrazine, quinoline, isoquinoline and their respective derivatives, or water molecule, alcohol molecule, ether, ketone, nitrile, ester, amide and their respective derivatives, or L 1 And L 2 Linked as a bidentate chelating ligand;
L 3 selected from carboxylic acid molecules and derivatives thereof, pyridine, imidazole, pyrazine, quinolineIsoquinoline and their respective derivatives, or water molecules, alcohol molecules, ethers, ketones, nitriles, esters, amides and their respective derivatives.
According to the invention, in formula II, L 1 And L 2 Preferably linked to pivalate, L 3 Isoquinoline is preferred.
According to the invention, the nitrile may be, for example, acetonitrile. Esters such as ethyl acetate; the amide is, for example, one of N-methylformamide, N-methylacetamide, N-dimethylformamide, and N, N-dimethylacetamide.
According to the present invention, the cluster having the structure represented by formula II is selected from any one of the following clusters 6 to 8:
cluster compound 6 of the formula Mn 4 YO 4 (R 1 CO 2 ) 8 (L 1 )(L 2 )(L 3 ) Wherein R is 1 = tert-butyl, L 1 And L 2 After ligation is pivalate (e.g., trimethylacetate, i.e., R in formula II-1) 2 Is tert-butyl), L 3 = isoquinoline.
Preferably, the cluster compound 6 is a single crystal; the structure is shown as formula II-1:
Figure BDA0003225650070000042
the single crystal belongs to a monoclinic system, and the space group is P2 1 N, unit cell parameter of
Figure BDA0003225650070000043
Figure BDA0003225650070000044
α =90.00 °, β =101.6590 (10) °, γ =90.00 °, Z =4, and volume
Figure BDA0003225650070000045
Cluster compound 7 of the formula Mn 4 GdO 4 (R 1 CO 2 ) 8 (L 1 )(L 2 )(L 3 ) Wherein R is 1 = tert-butyl, L 1 And L 2 After ligation is pivalate (e.g., trimethylacetate, i.e., R in formula II-2) 2 Is tert-butyl), L 3 = isoquinoline.
Preferably, the cluster compound 7 is a single crystal; the structure is shown as formula II-2:
Figure BDA0003225650070000046
the single crystal belongs to monoclinic system, and the space group is P2 1 N, unit cell parameter of
Figure BDA0003225650070000047
Figure BDA0003225650070000048
α =90.00 °, β =101.799 (2) °, γ =90.00 °, Z =4, and volume
Figure BDA0003225650070000049
Cluster 8 of the formula Mn 4 LuO 4 (R 1 CO 2 ) 8 (L 1 )(L 2 )(L 3 ) Wherein R is 1 = tert-butyl, L 1 And L 2 After ligation is pivalate (e.g., trimethylacetate, i.e., R in formula II-3) 2 Is tert-butyl), L 3 = isoquinoline.
Preferably, the cluster 8 is a single crystal; the structure is shown as formula II-3:
Figure BDA0003225650070000051
the single crystal belongs to a monoclinic system, and the space group is P2 1 N, unit cell parameter of
Figure BDA0003225650070000052
Figure BDA0003225650070000053
α =90.00 °, β =101.7670 (10) °, γ =90.00 °, Z =4, volume of
Figure BDA0003225650070000054
According to a specific embodiment of the present invention, the cluster compound has the chemical formula Mn 4 XO 5 H(R 1 CO 2 ) 8 (L 4 )(L 5 ) Has a structure shown in formula III, and contains four Mn ions and one rare earth ion which are connected into [ Mn ] through five mu-O 4 XO 5 ]Heteronuclear metal cluster framework cores; [ Mn ] 4 XO 5 ]The peripheral ligand of the heteronuclear metal cluster skeleton core is formed by eight carboxylate anions R 1 CO 2 - And two ligands L 4 And L 5 Providing; [ Mn ] 4 XO 5 ]The heteronuclear metal cluster skeleton core has one mu 2 -an O-bridge; the valence states of the four manganese ions are +3, +3, +4, +4;
Figure BDA0003225650070000055
in formula III, rare earth ions X, R 1 Has the meaning as above; l is 4 And L 5 Identical or different, independently of one another, from the group consisting of carboxylic acid molecules and derivatives thereof, pyridine, imidazole, pyrazine, quinoline, isoquinoline and respective derivatives thereof, or water molecules, alcohol molecules, ethers, ketones, nitriles, esters, amides and respective derivatives thereof, or L 4 And L 5 The linkage is a bidentate chelating ligand.
According to the invention, in formula III, L 4 、L 5 Identical or different, independently of one another, from the group consisting of N, N-dimethylacetamide, N, N-dimethylformamide, N-methylformamide.
Preferably, the cluster having the structure shown in formula III is selected from any one of the following clusters 9 to 11:
cluster 9 of the formula Mn 4 YO 5 H(RCO 2 ) 8 (L 4 )(L 5 ) Wherein R is 1 = tert-butyl; l is 4 、L 5 Are all N, N-dimethylacetamide.
Preferably, the cluster 9 is a single crystal; the structure is shown as formula III-1:
Figure BDA0003225650070000056
the single crystal belongs to an orthorhombic system, the space group is Pbca, and the unit cell parameter is
Figure BDA0003225650070000057
Figure BDA0003225650070000058
α =90 °, β =90 °, γ =90 °, Z =8, and a volume of
Figure BDA0003225650070000059
Cluster 10 of the formula Mn 4 DyO 5 H(RCO 2 ) 8 (L 4 )(L 5 ) Wherein R is 1 = tert-butyl; l is 4 、L 5 Are all N, N-dimethylacetamide.
Preferably, the cluster 10 is a single crystal; the structure is shown as formula III-2:
Figure BDA0003225650070000061
the single crystal belongs to an orthorhombic system, the space group is Pbca, and the unit cell parameter is
Figure BDA0003225650070000062
Figure BDA0003225650070000063
α =90 °, β =90 °, γ =90 °, Z =8, and a volume of
Figure BDA0003225650070000064
Cluster 11 of the formula Mn 4 LuO 5 H(RCO 2 ) 8 (L 4 )(L 5 ) Wherein R is 1 = tert-butyl; l is 4 、L 5 Are all N, N-dimethylacetamide.
Preferably, the cluster 11 is a single crystal; the structure is shown as formula III-3:
Figure BDA0003225650070000065
the single crystal belongs to an orthorhombic system, the space group is Pbca, and the unit cell parameter is
Figure BDA0003225650070000066
Figure BDA0003225650070000067
α =90 °, β =90 °, γ =90 °, Z =8, and a volume of
Figure BDA0003225650070000068
The invention also provides a preparation method of the rare earth manganese heteronuclear metal cluster compound, which comprises the following steps: and (2) reacting the permanganate anion type oxidant, the rare earth salt and the ligand, optionally adding water or a divalent manganese salt, in a solution to prepare the cluster compound.
In one embodiment, the present invention provides a composition having the structure of formula I and having the chemical formula Mn 3 XO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 The method for preparing a cluster compound of (1), which comprises the steps of:
reacting an organic carboxylic acid R 1 COOH, permanganate anion type oxidant, rare earth salt, water or bivalent manganese salt are optionally added, and the cluster compound is prepared by reaction in acetonitrile solution.
According to the invention, the method specifically comprises: reacting an organic carboxylic acid R 1 COOH, permanganate radical anion type oxidant, rare earth salt and water react in acetonitrile solution to obtain Mn as chemical formula with structure as shown in formula I 3 XO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 The cluster compound of (1).
According to the invention, the method specifically comprises: reacting an organic carboxylic acid R 1 COOH, permanganate radical anion type oxidant, rare earth salt and divalent manganese salt react in acetonitrile solution to obtain Mn with the structure shown in formula I 3 XO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 The cluster compound of (1).
According to the invention, the organic carboxylic acid R 1 The mol ratio of COOH, permanganate radical anion type oxidant, rare earth salt, water or bivalent manganese salt is (10-120): (1-10): 1: (0-5); preferably (20-120), (2-8) and (1-2).
According to the invention, the organic carboxylic acid R 1 COOH is selected from at least one of carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, and caproic acid, and derivatives thereof, and is preferably isobutyric acid or pivalic acid.
According to the invention, the permanganate anionic oxidizing agent is, for example, tetrabutylammonium permanganate ((C) 4 H 9 ) 4 N·MnO 4 )。
According to the invention, the rare earth salt can be at least one of triflate, nitrate, perchlorate, carboxylate and the like of rare earth ions, or the rare earth salt also contains crystal water; wherein the carboxylate of rare earth ions contains carboxylate anion (R) 1 CO 2 - ) The carboxylate anion has the aforementioned definition.
According to the invention, the manganous salt has the following structural formula: mnA 2 ·tH 2 O; wherein A is selected from carboxylate anions (R) 1 CO 2 - ) Chloride ion, clO 4 - 、NO 3 - 、CF 3 SO 3 - Acetylacetonate, the carboxylate anion having the meaning as previously described; t is 0 to 6, preferably 1 to 5, more preferably 2 to 4.
For example, the divalent manganese salt is selected from Mn (ClO) 4 ) 2 ，MnCl 2 ，Mn(NO 3 ) 2 ，Mn(CF 3 SO 3 ) 2 Manganese acetylacetonate, or a crystal water-containing manganese salt of each of them.
According to the invention, 60 to 100ml of acetonitrile are used per millimole of rare earth salt.
The inventors found that the chemical formula of the compound having the structure shown in formula I is Mn 3 XO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 The preparation method of the cluster compound can only be carried out in an acetonitrile solvent, and the target cluster compound cannot be obtained in alcohol or other organic solvents.
According to the invention, the reaction temperature is 60-90 ℃. For example, the temperature may be 60 ℃, 70 ℃,80 ℃ and 90 ℃.
According to the invention, the reaction time may be 10 to 60 minutes.
According to the invention, the reaction further comprises a post-treatment step: filtering the reaction product to remove precipitate, standing the reaction product to obtain purified Mn with a structure shown in formula I 3 XO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 The cluster compound of (1).
Illustratively, the rest period is, for example, 1 to 7 days.
As a preferred embodiment of the present invention, the chemical formula with the structure shown in formula I is Mn 3 XO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 The preparation method of the cluster compound comprises the following specific steps:
reacting an organic carboxylic acid R 1 COOH, permanganate radical anion type oxidant, rare earth salt and water react in acetonitrile solution for 10-60 min in the molar ratio of 10-120 to 1-10 to 1-5 to obtain brown solution, which is filteredRemoving the precipitate; standing for 1-7 days to obtain black crystals, namely Mn with the chemical formula shown in formula I 3 XO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 The cluster compound of (1).
As a preferred embodiment of the present invention, the chemical formula having the structure shown in formula I is Mn 3 XO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 The preparation method of the cluster compound comprises the following specific steps:
reacting an organic carboxylic acid R 1 COOH, permanganate radical anion type oxidant, rare earth salt and bivalent manganese salt react in acetonitrile solution for 10-60 min according to the molar ratio of (10-120) to (1-10) to (0-5) to obtain brown solution, and the brown solution is filtered to remove the precipitate; standing to obtain black crystals, namely Mn with the chemical formula shown in formula I 3 XO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 The cluster compound of (1).
According to a preferred embodiment of the present invention, cluster 1 has a molecular formula of C 60 H 111 Mn 3 O 26 Y is Mn 3 YO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 Wherein R is 1 = tert-butyl group.
Cluster compound 1 is a single crystal; the single crystal belongs to a triclinic system, the space group is P-1, and the unit cell parameter is
Figure BDA0003225650070000071
Figure BDA0003225650070000072
α =77.526 (3) °, β =87.004 (2) °, γ =65.818 (3) °, Z =2, and has a volume of
Figure BDA0003225650070000073
The structure is shown as formula I-1, the crystal structure is shown in figure 1, and the single crystal parameters are shown in table 1.
Table 1: single Crystal parameter of Cluster Compound 1
Figure BDA0003225650070000074
Figure BDA0003225650070000081
According to a preferred embodiment of the present invention, cluster 2 has a molecular formula of C 60 H 111 LaMn 3 O 26 Of the chemical formula Mn 3 LaO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 Wherein R is 1 = tert-butyl.
Cluster 2 is a single crystal; the single crystal belongs to a monoclinic system, and the space group is P2 1 N, unit cell parameter of
Figure BDA0003225650070000082
Figure BDA0003225650070000083
α =90 °, β =107.516 (4) °, γ =90 °, Z =4, and volume
Figure BDA0003225650070000084
The structure is shown in formula I-2, the crystal structure is shown in figure 2, and the single crystal parameters are shown in table 2.
Table 2: single Crystal parameter of Cluster 2
Figure BDA0003225650070000085
Figure BDA0003225650070000091
According to a preferred embodiment of the present invention, cluster 3 has a molecular formula of C 60 H 111 GdMn 3 O 26 Of the chemical formula Mn 3 GdO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 Wherein R is 1 = tert-butyl.
Cluster 3 is a single crystal; the single crystal belongs to a triclinic system, the space group is P-1, and the unit cell parameter is
Figure BDA0003225650070000092
Figure BDA0003225650070000093
α =77.898 (2) °, β =87.087 (2) °, γ =65.755 (2) °, Z =2, and has a volume of
Figure BDA0003225650070000094
The structure is shown as formula I-3, the crystal structure is shown as figure 3, and the single crystal parameters are shown as table 3.
Table 3: single crystal parameters of Cluster 3
Figure BDA0003225650070000095
Figure BDA0003225650070000101
According to a preferred embodiment of the present invention, cluster 4 has a molecular formula of C 60 H 111 DyMn 3 O 26 Of the chemical formula Mn 3 DyO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 Wherein R is 1 = tert-butyl group.
Cluster 4 is a single crystal; the single crystal belongs to a triclinic system, the space group is P-1, and the unit cell parameter is
Figure BDA0003225650070000102
Figure BDA0003225650070000103
α =77.790 (2) °, β =86.995 (2) °, γ =65.678 (2) °, Z =2, and has a volume of
Figure BDA0003225650070000104
The structure is shown as formula I-4, the crystal structure is shown in figure 4, and the single crystal parameters are shown in table 4.
Table 4: single crystal parameter of cluster 4
Figure BDA0003225650070000105
According to a preferred embodiment of the present invention, cluster 5 has a molecular formula of C 60 H 111 LuMn 3 O 26 Of the chemical formula Mn 3 LuO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 Wherein R is 1 = tert-butyl group.
Cluster 5 is a single crystal; the single crystal belongs to a triclinic system, the space group is P-1, and the unit cell parameter is
Figure BDA0003225650070000106
Figure BDA0003225650070000107
α =77.450 (3) °, β =87.291 (3) °, γ =65.954 (3) °, Z =2, and has a volume of
Figure BDA0003225650070000108
The structure is shown in formula I-5, the crystal structure is shown in figure 5, and the single crystal parameters are shown in table 5.
Table 5: single crystal parameters of Cluster 5
Figure BDA0003225650070000111
In one embodiment, the present invention also provides a composition having the structure of formula II and having the chemical formula Mn 4 XO 4 (R 1 CO 2 ) 8 (L 1 )(L 2 )(L 3 ) The method for preparing the cluster compound specifically comprises the following steps:
(1) Reacting an organic carboxylic acid R 1 COOH, permanganateReacting an anionic oxidant, a divalent manganese salt and a rare earth salt in an acetonitrile solution to prepare an intermediate;
(2) The intermediate in the step (1) is reacted with a ligand L 3 Reaction, optionally with ligand L 1 And/or L 2 Reacting to obtain Mn with a chemical formula shown as a formula II 4 XO 4 (R 1 CO 2 ) 8 (L 1 )(L 2 )(L 3 ) The cluster compound of (1);
wherein the organic carboxylic acid R 1 COOH, permanganate radical anionic oxidizing agent, divalent manganese salt, rare earth salt and L 1 、L 2 And L 3 Has the meaning as above.
According to the invention, the organic carboxylic acid R 1 The molar ratio of COOH, permanganate radical anion type oxidant, divalent manganese salt and rare earth salt is (10-120): (1-10): 1:1, preferably (20-100): 2-8): 1:1.
In the method, the content of acetonitrile used in each millimole of rare earth salt is about 60-100 ml. The reaction can only be carried out in acetonitrile solvent, and the target cluster compound can not be obtained in alcohol or other organic solvents.
According to the invention, in the step (2), the intermediate is firstly dissolved in a halogenated hydrocarbon organic solvent and a nitrile solvent, and then reacts with the ligand.
According to the invention, in the step (2), the halogenated hydrocarbon organic solvent can be one of dichloromethane, dichloroethane or chloroform and derivatives thereof; the nitrile solvent may be acetonitrile, propionitrile or butyronitrile and one of its derivatives.
According to the invention, in step (2), the ligand accounts for 0.1-3% of the total volume of the solvent.
According to the invention, in the step (1), the method further comprises the following post-processing steps: filtering the intermediate to remove the precipitate, and standing the intermediate at 0 ℃ to obtain a solid, namely the purified intermediate.
According to the invention, in the step (2), the method further comprises the following post-processing steps: filtering the reaction product to remove precipitate, standing the reaction product to separate out crystals, washing and drying the crystals to obtain the purified Mn with the chemical formula shown in formula II 4 XO 4 (R 1 CO 2 ) 8 (L 1 )(L 2 )(L 3 ) The cluster compound of (1).
Illustratively, the rest period is, for example, 1 to 7 days.
According to the invention, the reaction temperature is 60 ℃ to 90 ℃.
According to the invention, the reaction time may be 10 to 60 minutes.
According to a preferred scheme of the invention, the preparation method specifically comprises the following steps:
the first step is as follows: reacting an organic carboxylic acid R 1 COOH, permanganate acid radical anion type oxidant, divalent manganese salt and rare earth salt, according to the molar ratio of (10-120): 1-10): 1:1, heating and reacting in acetonitrile solution for 10-60 minutes to obtain brown solution, filtering and removing precipitate; standing for 1-6 days at 0 ℃ to obtain brown crystals, namely intermediates;
the second step: dissolving the synthetic intermediate in the mixed solvent of halogenated hydrocarbon organic solvent and nitrile, adding ligand L 3 Further reaction, optionally with a ligand L 1 And/or L 2 Reacting and crystallizing to obtain the cluster compound with the structure shown in the formula (II).
According to a preferred embodiment of the present invention, cluster 6 has the formula C 54 H 88 Mn 4 NO 22 Y is Mn 4 YO 4 (R 1 CO 2 ) 9 (C 9 H 7 N), wherein R 1 = tert-butyl.
Cluster compound 6 is a single crystal; the single crystal belongs to a monoclinic system, and the space group is P2 1 N, unit cell parameter of
Figure BDA0003225650070000121
Figure BDA0003225650070000122
α =90.00 °, β =101.6590 (10) °, γ =90.00 °, Z =4, and volume
Figure BDA0003225650070000123
The structure is shown as formula II-1, the crystal structure is shown in figure 6, singlyThe crystal parameters are shown in Table 6.
Table 6: single crystal parameters of Cluster 6
Figure BDA0003225650070000124
Figure BDA0003225650070000131
According to a preferred embodiment of the present invention, cluster 7 has a molecular formula of C 54 H 88 GdMn 4 NO 22 Of the chemical formula Mn 4 GdO 4 (R 1 CO 2 ) 9 (C 9 H 7 N), wherein R 1 = tert-butyl group.
Cluster 7 is a single crystal. The single crystal belongs to a monoclinic system, and the space group is P2 1 N, unit cell parameter of
Figure BDA0003225650070000132
Figure BDA0003225650070000133
α =90.00 °, β =101.799 (2) °, γ =90.00 °, Z =4, volume of
Figure BDA0003225650070000134
Figure BDA0003225650070000135
The structure is shown as formula II-2, the crystal structure is shown as figure 7, and the single crystal parameters are shown as table 7.
Table 7: single crystal parameters of Cluster 7
Figure BDA0003225650070000136
Figure BDA0003225650070000141
According to a preferred embodiment of the present invention, cluster 8 has a molecular formula of C 54 H 88 LuMn 4 NO 22 Of the chemical formula Mn 4 LuO 4 (R 1 CO 2 ) 9 (C 9 H 7 N), wherein R 1 = tert-butyl group.
Cluster 8 is a single crystal; the single crystal belongs to a monoclinic system, and the space group is P2 1 N, unit cell parameter of
Figure BDA0003225650070000142
Figure BDA0003225650070000143
α =90.00 °, β =101.7670 (10) °, γ =90.00 °, Z =4, and volume
Figure BDA0003225650070000144
The structure is shown in formula II-3, the crystal structure is shown in figure 8, and the single crystal parameters are shown in table 8.
Table 8: single crystal parameters of Cluster 8
Figure BDA0003225650070000145
In one embodiment, the present invention also provides a composition having the structure of formula III and having the chemical formula Mn 4 XO 5 H(R 1 CO 2 ) 8 (L 4 )(L 5 ) The method for producing a cluster compound of (1), the method comprising:
dissolving cluster compound with structure shown in formula II in halogenated hydrocarbon and/or ester solvent, adding water, optionally adding or not adding ligand L 4 And a ligand L 5 And reacting to obtain the cluster compound with the structure shown in III.
According to the present invention, the ester solvent may be one of methyl acetate, ethyl acetate, and the like.
Wherein, halogenated hydrocarbon, ligand L 4 、L 5 Has the meaning as above.
According to the invention, the preparation method further comprises a post-treatment step: filtering the reaction product, removing a few precipitates, standing the reaction solution, washing precipitated crystals by n-hexane, drying, and preparing the purified Mn with the structure shown in formula III and the chemical formula 4 XO 5 H(R 1 CO 2 ) 8 (L 4 )(L 5 ) The cluster compound of (1).
According to the invention, the reaction temperature is 20-60 ℃.
According to the invention, the reaction time may be between 1 and 15 minutes.
According to a preferred embodiment of the present invention, cluster 9 has a molecular formula of C 48 H 91 Mn 4 N 2 O 23 Y is Mn 4 YO 5 H(R 1 CO 2 ) 8 (L 4 )(L 5 ) Wherein R is 1 = tert-butyl; l is 4 、L 5 Are all N, N-dimethylacetamide.
Cluster 9 is a single crystal; the single crystal belongs to an orthorhombic system, the space group is Pbca, and the unit cell parameter is
Figure BDA0003225650070000151
Figure BDA0003225650070000152
α =90 °, β =90 °, γ =90 °, Z =8, and a volume of
Figure BDA0003225650070000153
The structure is shown in formula III-1, the crystal structure is shown in figure 9, and the single crystal parameters are shown in table 9.
Table 9: single crystal parameters of Cluster 9
Figure BDA0003225650070000154
Figure BDA0003225650070000161
According to a preferred embodiment of the present invention, cluster 10 has a molecular formula of C 48 H 91 DyMn 4 N 2 O 23 Of the chemical formula Mn 4 DyO 5 H(R 1 CO 2 ) 8 (L 4 )(L 5 ) Wherein R is 1 = tert-butyl; l is 4 、L 5 Are all N, N-dimethylacetamide.
Cluster 10 is a single crystal. The single crystal belongs to an orthorhombic system, the space group is Pbca, and the unit cell parameter is
Figure BDA0003225650070000162
Figure BDA0003225650070000163
α =90 °, β =90 °, γ =90 °, Z =8, and has a volume of
Figure BDA0003225650070000164
The structure is shown in formula III-2, the crystal structure is shown in figure 10, and the single crystal parameters are shown in table 10.
Table 10: single crystal parameters of cluster 10
Figure BDA0003225650070000165
According to a preferred embodiment of the present invention, cluster 11 has a molecular formula of C 48 H 91 Mn 4 N 2 O 23 Lu of the chemical formula Mn 4 LuO 5 H(R 1 CO 2 ) 8 (L 4 )(L 5 ) Wherein R is 1 = tert-butyl; l is 4 、L 5 Are all N, N-dimethylacetamide.
Cluster 11 is a single crystal; the single crystal belongs to an orthorhombic system, the space group is Pbca, and the unit cell parameter is
Figure BDA0003225650070000166
Figure BDA0003225650070000167
α =90 °, β =90 °, γ =90 °, Z =8, and a volume of
Figure BDA0003225650070000168
The structure is shown in formula III-3, the crystal structure is shown in figure 11, and the single crystal parameters are shown in table 11.
Table 11: single crystal parameter of cluster 11
Figure BDA0003225650070000171
The invention also provides a bionic water cracking catalyst, which contains the rare earth manganese heteronuclear metal cluster compound.
The invention also provides application of the bionic water cracking catalyst to catalytic water cracking.
According to the invention, the catalytic process is carried out at the surface of the electrode or in the presence of an oxidizing agent.
The invention has the beneficial effects that:
the invention introduces rare earth ions X with stronger coordination capability to synthesize a series of rare earth ions with [ Mn n XO m ]Clusters of heteronuclear metal cluster skeletal cores, e.g. having a core structure of [ Mn ] 3 XO 2 ]、[Mn 4 XO 4 ]And [ Mn 4 XO 5 ]The cluster compound of (1). The series of cluster compounds are novel bionic water cracking catalysts. In particular a core structure of [ Mn 4 XO 4 ]And [ Mn 4 XO 5 ]The geometrical structure and Mn ion valence state of the cluster compound are very similar to those of a biological water cracking catalytic center. The series of novel bionic cluster compounds containing rare earth break through the traditional concept, are not limited to alkaline earth metal which is completely the same as organisms, the stability of the bionic cluster compounds is greatly improved by introducing rare earth metal ions, and the catalytic cracking of water is driven by the presence of an oxidant (either a stable oxidant or a transient oxidant generated by light induction) on the surface of an electrode. In addition, the unique magnetic characteristics of tetravalent Mn ions and some rare earth elements in the cluster compound are combined, the important application value is realized in the aspect of magnetic materials, and the spectral tracking is combinedThe characteristics and the like can lay an important foundation for mechanism research in the future.
(1) In the present invention, structurally, the trivalent rare earth ion X-containing [ Mn [ ] 3 XO 2 ]、[Mn 4 XO 4 ]、[Mn 4 XO 5 ]Cluster compound and [ Mn ] containing divalent alkaline earth metal ion 4 CaO 4 ]、[Mn 4 SrO 4 ]Compared with the cluster compound, the introduction of the trivalent rare earth ions obviously increases the stability of the cluster compound, and simultaneously can more stably carry out catalytic water cracking. Furthermore, since the alkaline earth or rare earth ions are all in the core of the cluster compound, there is no possibility of them being interchanged without destroying the overall structure. The charges of alkaline earth and rare earth metal ions, pKa values of hydrated ions and the like are obviously different, and the differences can cause great differences in the structure and the performance of the final product.
(2) The method adopts rare earth ions, manganese ions and carboxylic acid as raw materials, taking permanganate anions as an oxidant, synthesizing to obtain a core structure of [ Mn ] 3 XO 2 ]、[Mn 4 XO 4 ]And [ Mn 4 XO 5 ]The valence of the manganese ions of the clusters is +3 or +4, and the clusters have important value in the aspect of magnetic materials. In addition, the core structure obtained by the invention is [ Mn ] 4 XO 4 ]And [ Mn 4 XO 5 ]The cluster compound can be used as an artificial water cracking catalyst for catalytic cracking of water on the surface of an electrode or driven by an oxidant (which can be a stable oxidant or a transient oxidant generated by light induction).
In particular, the method comprises the following steps of,
1) The invention uses rare earth ions, water or divalent manganese salt, permanganate and simple organic carboxylic acid as initial raw materials to synthesize the material with the core structure of [ Mn 3 XO 2 ]The periphery of the cluster is provided with ligands by nine carboxylate anions and three neutral carboxylic acid molecules, wherein the valence states of the three manganese ions are +3, +3, +4 respectively. This mixed valence state containing [ Mn ] with ligands provided entirely by carboxylic acids 3 XO 2 ]Clusters have not been previously reported.
2) The invention utilizes rare earth ions and permanganateDivalent manganese ion (Mn) 2+ ) And simple organic carboxylic acids as starting materials, successfully achieved the utilization of simple metal ions (Mn) 2+ ,X 3+ Ionic), simple organic carboxylic acids and MnO 4 - As a starting material, a bionic core structure [ Mn ] is obtained by multi-step synthesis 4 XO 4 ]The cluster compound of (1). In the [ Mn ] 4 XO 4 ]In the cluster, [ Mn ] 3 XO 4 ]Cubic alkane and an outer Mn ion are bridged through mu-O to form [ Mn ] 4 XO 4 ]The core structure and the peripheral ligand are formed by eight carboxylate anions R 1 CO 2 - Ligand L 1 And L 2 And an exchangeable ligand L 3 And (4) forming. Wherein the valence states of the four manganese ions are +3, +3, +4, +4 respectively.
3) The invention adopts the cluster compound with the structure of the formula II to further react with water, and mu is successfully introduced into the core 2 -O-bridges, i.e. bidentate oxygen bridges, giving a biomimetic core structure of [ Mn [ ] 4 XO 5 ]The cluster compound of (1). Its peripheral ligands consist of eight carboxylate anions and two exchangeable ligands. Wherein the valence states of the four manganese ions are +3, +3, +4, +4 respectively. The cluster compound not only successfully simulates the ten-atom core skeleton and coordination environment of the biological OEC, but also simulates the oxidation-reduction characteristics of the biological OEC. In particular, the cluster compound can be used as a catalyst to stably perform catalytic water cracking reaction and release oxygen.
Drawings
FIG. 1 is a crystal structure diagram of cluster compound 1 prepared in example 1 of the present invention.
FIG. 2 is a crystal structure diagram of cluster compound 2 prepared in example 2 of the present invention.
FIG. 3 is a crystal structure diagram of cluster compound 3 prepared in example 3 of the present invention.
FIG. 4 is a crystal structure diagram of cluster compound 4 prepared in example 4 of the present invention.
FIG. 5 is a crystal structure diagram of cluster compound 5 prepared in example 5 of the present invention.
FIG. 6 is a crystal structure diagram of cluster compound 6 prepared in example 6 of the present invention.
FIG. 7 is a crystal structure diagram of cluster compound 7 prepared in example 7 of the present invention.
FIG. 8 is a crystal structure diagram of cluster compound 8 prepared in example 8 of the present invention.
FIG. 9 is a crystal structure diagram of cluster compound 9 prepared in example 9 of the present invention.
FIG. 10 is a crystal structure diagram of cluster compound 10 prepared in example 10 of the present invention.
FIG. 11 is a crystal structure diagram of cluster compound 11 prepared in example 11 of the present invention.
FIG. 12 is a UV-VIS absorption spectrum of 1,2- dichloroethane corresponding clusters 1,2, 3, 4 and 5 of example 12 of the present invention.
FIG. 13 is a UV-VIS absorption spectrum of 1,2-dichloroethane for corresponding clusters 6 and 8 of example 12 of the present invention.
FIG. 14 is a UV-VIS absorption spectrum of 1,2-dichloroethane for corresponding clusters 9 and 11 of example 12 of the present invention.
FIG. 15 is a graph of the catalytic water splitting current generated by the working electrode adsorbing clusters 6 in example 13.
FIG. 16 is a graph of the catalytic water splitting current generated by the working electrode adsorbing clusters 8 in example 13.
FIG. 17 is a graph of the catalytic water splitting current generated by the working electrode adsorbing clusters 9 in example 13.
FIG. 18 is a graph of the catalytic water splitting current generated by the working electrode of adsorbed cluster 11 in example 13.
FIG. 19 is a graph showing the catalytic stability of cluster 9 in example 13.
FIG. 20 is an oxygen test chart of cluster 9 catalyzed water splitting in example 13.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise specified, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
In examples 1-11, the core backbone and ligands are shown in the form of a bat and a line, respectively, with hydrogen atoms omitted, in order to clarify the structural formulae of clusters 1-11.
Example 1: cluster Compound 1,Mn 3 YO 2 (C 5 H 9 O 2 ) 9 (C 5 H 9 O 2 H) 3
The preparation method is selected from any one of the following methods:
scheme 1: tetrabutylammonium permanganate (Bu) was added to a 250ml round bottom flask n 4 NMnO 4 8 mmol), yttrium trifluoromethanesulfonate (Y (CF) 3 SO 3 ) 3 2 mmol), water (2 mmol) and pivalic acid (Bu) t CO 2 H,80 mmol) was left to react for 25 minutes in 80 ℃ acetonitrile, the reaction was stopped, a small amount of precipitate was removed by filtration, and the resulting brown mother liquor was allowed to stand at 2 ℃. After several days, black crystals precipitated. The resulting crystals were collected, washed with acetonitrile, and dried under vacuum with a yield of about 15% (based on moles of Y ion).
Scheme 2: tetrabutylammonium permanganate (Bu) was added to a 250ml round bottom flask n 4 NMnO 4 8 mmol), yttrium trifluoromethanesulfonate (Y (CF) 3 SO 3 ) 3 2 mmol), manganese (II) acetylacetonate (2 mmol) and pivalic acid (Bu) t CO 2 H,80 mmol) was left to react for 25 minutes in 80 ℃ acetonitrile, the reaction was stopped, a small amount of precipitate was removed by filtration, and the resulting brown mother liquor was allowed to stand at 2 ℃. After several days, black crystals precipitated. The resulting crystals were collected, washed with acetonitrile, and dried under vacuum in about 58% yield (based on moles of Y ion).
Cluster compound 1 of the formula Mn 3 YO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 Wherein R is 1 = tert-butyl.
I.e. cluster 1, of the formula Mn 3 YO 2 (C 5 H 9 O 2 ) 9 (C 5 H 9 O 2 H) 3 The molecular formula is as follows: c 60 H 111 Mn 3 O 26 And Y. Theoretical value (%) of elemental analysis is C,47.97; h,7.45; the experimental value (%): C,47.83; h,7.42. The single crystal belongs to a triclinic system, the space group is P-1, and the unit cell parameter is
Figure BDA0003225650070000191
α =77.526 (3) °, β =87.004 (2) °, γ =65.818 (3) °, Z =2, and has a volume of
Figure BDA0003225650070000192
The chemical structure of cluster 1 is shown in formula I-1, the measured specific parameters of single crystal are shown in Table 1, and the crystal space structure is shown in FIG. 1.
Figure BDA0003225650070000193
Example 2: cluster compound 2,Mn 3 LaO 2 (C 5 H 9 O 2 ) 9 (C 5 H 9 O 2 H) 3
The preparation of example 2 was carried out in the same manner as in 2 of example 1 except that lanthanum trifluoromethanesulfonate was used in place of yttrium trifluoromethanesulfonate. The yield was about 31% (in terms of moles of La ion).
Cluster 2 of the formula Mn 3 LaO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 Wherein R is 1 = tert-butyl group.
I.e., cluster 2, of the formula Mn 3 LaO 2 (C 5 H 9 O 2 ) 9 (C 5 H 9 O 2 H) 3 The molecular formula is as follows: c 60 H 111 LaMn 3 O 26 . Theoretical value (%) of elemental analysis C,46.43; h,7.21; the experimental value (%): C,46.38; h,7.14. The single crystal belongs to monoclinic system, and the space group is P2 1 N, unit cellParameter is
Figure BDA0003225650070000201
α =90 °, β =107.516 (4) °, γ =90 °, Z =4, and volume
Figure BDA0003225650070000202
The chemical structure of cluster 2 is shown in formula I-2 below, the measured specific parameters of the single crystal are shown in Table 2, and the crystal space structure is shown in FIG. 2.
Figure BDA0003225650070000203
Example 3: cluster Compound 3,Mn 3 GdO 2 (C 5 H 9 O 2 ) 9 (C 5 H 9 O 2 H) 3
Example 3 was prepared in the same manner as in example 1, except that gadolinium trifluoromethanesulfonate (Gd (CF) was used 3 SO 3 ) 3 ) Replacing yttrium trifluoromethanesulfonate. The yield was about 48% (based on moles of Gd ions).
Cluster 3 of the formula Mn 3 GdO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 Wherein R is 1 = tert-butyl.
I.e., cluster 3, of the formula Mn 3 GdO 2 (C 5 H 9 O 2 ) 9 (C 5 H 9 O 2 H) 3 The molecular formula is as follows: c 60 H 111 GdMn 3 O 26 . Theoretical value (%) of elemental analysis is C,45.88; h,7.12; the experimental value (%) is C,45.66; h,7.23. The single crystal belongs to a triclinic system, the space group is P-1, and the unit cell parameter is
Figure BDA0003225650070000204
α =77.898 (2) °, β =87.087 (2) °, γ =65.755 (2) °, Z =2, and has a volume of
Figure BDA0003225650070000205
The chemical structure of cluster 3 is shown in formula I-3 below, the measured specific parameters of the single crystal are shown in Table 3, and the crystal space structure is shown in FIG. 3.
Figure BDA0003225650070000206
Example 4: cluster Compound 4,Mn 3 DyO 2 (C 5 H 9 O 2 ) 9 (C 5 H 9 O 2 H) 3
Example 4 was prepared in the same manner as in example 1, except that dysprosium trifluoromethanesulfonate (Dy (CF) was used 3 SO 3 ) 3 ) Replacing yttrium trifluoromethanesulfonate. The yield was about 43% (in terms of moles of Dy ion).
Cluster compound 4 of the formula Mn 3 DyO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 Wherein R is 1 = tert-butyl group.
I.e., cluster 4, of the formula Mn 3 DyO 2 (C 5 H 9 O 2 ) 9 (C 5 H 9 O 2 H) 3 The molecular formula is as follows: c 60 H 111 DyMn 3 O 26 . Theoretical value of elemental analysis C,45.73; h,7.10; the experimental value is C,45.76; h,6.98. The single crystal belongs to a triclinic system, the space group is P-1, and the unit cell parameter is
Figure BDA0003225650070000207
α =77.790 (2) °, β =86.995 (2) °, γ =65.678 (2) °, Z =2, and has a volume of
Figure BDA0003225650070000208
The chemical structure of cluster 4 is shown in formula I-4 below, the measured parameters of the single crystal are shown in Table 4, and the crystal space structure is shown in FIG. 4.
Figure BDA0003225650070000209
Example 5: cluster 5,Mn 3 LuO 2 (C 5 H 9 O 2 ) 9 (C 5 H 9 O 2 H) 3
Example 5 was prepared in the same manner as in example 1, method 2, except that lutetium triflate (Lu (CF) was used 3 SO 3 ) 3 ) Replacing yttrium trifluoromethanesulfonate. The yield was about 48% (in terms of moles of Lu ions).
Cluster 5 of the formula Mn 3 LuO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 Wherein R is 1 = tert-butyl.
I.e. cluster 5, formula Mn 3 LuO 2 (C 5 H 9 O 2 ) 9 (C 5 H 9 O 2 H) 3 The molecular formula is as follows: c 60 H 111 LuMn 3 O 26 . The single crystal belongs to a triclinic system, the space group is P-1, and the unit cell parameter is
Figure BDA0003225650070000211
Figure BDA0003225650070000212
α =77.450 (3) °, β =87.291 (3) °, γ =65.954 (3) °, Z =2, and has a volume of
Figure BDA0003225650070000213
The chemical structure of cluster 5 is shown in formula I-5 below, the measured specific parameters of the single crystal are shown in Table 5, and the crystal space structure is shown in FIG. 5.
Figure BDA0003225650070000214
Example 6: cluster Compound 6,Mn 4 YO 4 (C 5 H 9 O 2 ) 9 (C 9 H 7 N)
The preparation method comprises the following steps:
in the first step, ammonium tetrabutyl permanganate (Bu) was added to a 100ml round bottom flask n 4 NMnO 4 4 mmol), yttrium trifluoromethanesulfonate (Y (CF) 3 SO 3 ) 3 1 mmol), manganese acetylacetonate (Mn (acac) 2 ) 1 mmol) and pivalic acid ((CH) 3 ) 3 CCO 2 H,40 mmol) was left to react for 25 minutes in 80 ℃ acetonitrile, the reaction was stopped, a small amount of precipitate was removed by filtration, and the resulting brown mother liquor was left to stand at 2 ℃ for several days, whereupon a brown synthetic intermediate was precipitated.
In the second step, the intermediate obtained is dissolved in dichloromethane and acetonitrile (the volume ratio is 1:2), isoquinoline accounting for 1 percent of the total volume is added, and brown crystals are separated out after several days. The resulting crystals were collected, washed with n-hexane, and dried under vacuum with a yield of-19% (based on moles of Y ion).
Cluster compound 6 of the formula Mn 4 YO 4 (R 1 CO 2 ) 9 (L 3 ) Wherein R is 1 = tert-butyl, L 3 = isoquinoline.
I.e. cluster 6, of the formula Mn 4 YO 4 (C 5 H 9 O 2 ) 9 (C 9 H 7 N), molecular formula: c 54 H 88 Mn 4 NO 22 And Y. Theoretical value of elemental analysis (%): C,45.94; h,6.28; n,0.99; the experimental value (%): C,46.19; h,6.27; and N,1.01. The single crystal belongs to a monoclinic system, and the space group is P2 1 N, unit cell parameter of
Figure BDA0003225650070000215
α =90.00 °, β =101.6590 (10) °, γ =90.00 °, Z =4, and volume
Figure BDA0003225650070000216
The chemical structure of cluster compound 6 is shown in formula II-1 below, the measured parameters of its single crystal are shown in Table 6, and the crystal space structure is shown in FIG. 6.
Figure BDA0003225650070000217
Example 7: cluster compound 7,Mn 4 GdO 4 (C 5 H 9 O 2 ) 9 (C 9 H 7 N)
The preparation method comprises the following steps:
in the first step, ammonium tetrabutylpermanganate (Bu) was added to a 100ml round bottom flask n 4 NMnO 4 8 mmol), gadolinium trifluoromethanesulfonate (Gd (CF) 3 SO 3 ) 3 2 mmol), manganese (II) acetylacetonate (Mn (acac) 2 ) 2 mmol) and pivalic acid ((CH) 3 ) 3 CCO 2 H,80 mmol) was left to react for 25 minutes in 80 ℃ acetonitrile, the reaction was stopped, a small amount of precipitate was removed by filtration, and the resulting brown mother liquor was left to stand at 2 ℃ for several days, after which a brown synthetic intermediate was precipitated.
And secondly, dissolving the obtained intermediate in dichloromethane and acetonitrile (the volume ratio is 1:2), adding isoquinoline with the volume ratio of 1 percent, and precipitating brown crystals after several days.
Cluster compound 7 of the formula Mn 4 GdO 4 (R 1 CO 2 ) 9 (L 3 ) Wherein R is 1 = tert-butyl, L 3 = isoquinoline.
I.e. cluster 7, of the formula Mn 4 GdO 4 (C 5 H 9 O 2 ) 9 (C 9 H 7 N), molecular formula: c 54 H 88 GdMn 4 NO 22 . The single crystal belongs to a monoclinic system, and the space group is P2 1 N, unit cell parameter of
Figure BDA0003225650070000221
Figure BDA0003225650070000222
α =90.00 °, β =101.799 (2) °, γ =90.00 °, Z =4, volume of
Figure BDA0003225650070000223
The chemical structure of cluster 7 is shown in formula II-2 below, the measured parameters of its single crystal are shown in Table 7, and the crystal space structure is shown in FIG. 7.
Figure BDA0003225650070000224
Example 8: cluster 8,Mn 4 LuO 4 (C 5 H 9 O 2 ) 9 (C 9 H 7 N)
Example 8 Cluster 8 was prepared in the same manner as in example 6, except that lutetium triflate (Lu (CF) was used 3 SO 3 ) ) was substituted for yttrium trifluoromethanesulfonate in example 6.
Cluster 8 of the formula Mn 4 LuO 4 (R 1 CO 2 ) 9 (L 3 ) Wherein R is 1 = tert-butyl, L 3 = isoquinoline.
I.e. cluster 8, of the formula Mn 4 LuO 4 (C 5 H 9 O 2 ) 9 (C 9 H 7 N), molecular formula: c 54 H 88 LuMn 4 NO 22 . Theoretical value (%) of elemental analysis C,43.30; h,5.92; n,0.94; the experimental value (%): C,43.69; h,5.96; n,0.90. The single crystal belongs to a monoclinic system, and the space group is P2 1 N, unit cell parameter of
Figure BDA0003225650070000225
Figure BDA0003225650070000226
α =90.00 °, β =101.7670 (10) °, γ =90.00 °, Z =4, and volume
Figure BDA0003225650070000227
The chemical structure of cluster 8 is shown in formula II-3 below, the measured parameters of its single crystal are shown in Table 8, and the crystal space structure is shown in FIG. 8.
Figure BDA0003225650070000228
Example 9: cluster 9,Mn 4 YO 5 H(C 5 H 9 O 2 ) 8 (C 4 H 9 NO) 2
The preparation method comprises the following steps:
adding Mn as shown in formula II-1 4 YO 4 (C 5 H 9 O 2 ) 9 (C 9 H 7 N) was dissolved in dichloromethane and ethyl acetate (3:1 by volume) and 5% N, N-dimethylacetamide (by volume) and water (water and Mn) were added 4 YO 4 (C 5 H 9 O 2 ) 9 (C 9 H 7 N) is 2:1), reacting for 5min at 40 ℃, filtering the reaction product, removing a few precipitates, standing the reaction liquid, and separating out brown crystals after several days. The resulting crystals were collected, washed with n-hexane and dried under vacuum to give a yield of about 52% (in terms of moles of Y ion).
Cluster 9 of the formula [ Mn 4 YO 5 ]H(RCO 2 ) 8 (L 4 )(L 5 ) Wherein R is 1 = tert-butyl; l is 4 、L 5 Are all N, N-dimethylacetamide.
I.e. cluster 9, of the formula Mn 4 YO 5 H(C 5 H 9 O 2 ) 8 (C 4 H 9 NO) 2 The molecular formula is as follows: h 91 C 48 N 2 O 23 Mn 4 And Y. Theoretical value (%) of elemental analysis is C,39.97; h,6.41; n,2.33; the experimental value (%): C,40.08; h,6.39; n,2.33. The single crystal belongs to an orthorhombic system, the space group is Pbca, and the unit cell parameter is
Figure BDA0003225650070000229
Figure BDA00032256500700002210
α =90 °, β =90 °, γ =90 °, Z =8, and a volume of
Figure BDA00032256500700002211
The chemical structure of cluster 9 is shown in formula III-1 below, the measured specific parameters of the single crystal are shown in Table 9, and the crystal space structure is shown in FIG. 9.
Figure BDA0003225650070000231
Example 10: cluster 10,Mn 4 DyO 5 H(C 5 H 9 O 2 ) 8 (C 4 H 9 NO) 2
The preparation method comprises the following steps:
Mn 4 DyO 5 H(C 5 H 9 O 2 ) 8 (C 4 H 9 NO) 2 synthetic scheme of (2) and Mn 4 YO 5 H(C 5 H 9 O 2 ) 8 (C 4 H 9 NO) 2 Similarly, only yttrium triflate in the synthesis raw material needs to be replaced by dysprosium triflate (Dy (CF) 3 SO 3 ) 3 )。
Cluster 10 of the formula Mn 4 DyO 5 H(RCO 2 ) 8 (L 4 )(L 5 ) Wherein R is 1 = tert-butyl; l is 4 、L 5 Are all N, N-dimethylacetamide.
I.e., cluster 10, of the formula Mn 4 DyO 5 H(C 5 H 9 O 2 ) 8 (C 4 H 9 NO) 2 . The single crystal is orthorhombic, the space group is Pbca, and the unit cell parameter is
Figure BDA0003225650070000232
α =90 °, β =90 °, γ =90 °, Z =8, and a volume of
Figure BDA0003225650070000233
The chemical structure of cluster 10 is shown in formula III-2 below, the measured parameters of its single crystal are shown in Table 10, and the crystal space structure is shown in FIG. 10.
Figure BDA0003225650070000234
Example 11: cluster 11,Mn 4 LuO 5 H(C 5 H 9 O 2 ) 8 (C 4 H 9 NO) 2
The preparation method comprises the following steps:
Mn 4 LuO 5 H(C 5 H 9 O 2 ) 8 (C 4 H 9 NO) 2 synthetic scheme of (2) and Mn 4 YO 5 H(C 5 H 9 O 2 ) 8 (C 4 H 9 NO) 2 Similarly, only yttrium triflate in the starting material needs to be replaced by lutetium triflate. Brown crystals precipitated after several days. The resulting crystals were collected, washed with n-hexane, and dried under vacuum with a yield of 39% (based on moles of Lu ions).
Cluster 11 of the formula Mn 4 LuO 5 H(RCO 2 ) 8 (L 4 )(L 5 ) Wherein R is 1 Is tert-butyl; l is 4 、L 5 Are all N, N-dimethylacetamide.
I.e., cluster 11, of the formula Mn 4 LuO 5 H(C 5 H 9 O 2 ) 8 (C 4 H 9 NO) 2 ·(C 2 H 5 NO) 0.5 (Note: the presence of N, N-dimethylacetamide solvent molecules), formula: h 95.5 C 50 N 2.5 O 23.5 Mn 4 Lu. Theoretical value (%) of element analysis is C,39.99; h,6.41; n,2.33; the experimental value (%): C,40.08; h,6.39; n,2.33. The single crystal is orthorhombic, the space group is Pbca, and the unit cell parameter is
Figure BDA0003225650070000235
α =90 °, β =90 °, γ =90 °, Z =8, and a volume of
Figure BDA0003225650070000236
Figure BDA0003225650070000237
The chemical structure of the cluster compound 11 is shown as a formula III-3, specific single crystal measurement parameters are shown in a table 11, and a crystal space structure is shown in a table 11.
Experimental example 12: ultraviolet-visible absorption spectra of clusters 1,2, 3, 4, 5, 6, 8, 9, and 11
A20 μ M solution of 1,2-dichloroethane corresponding to the cluster compound was added to a 10mm optical path quartz cuvette and the absorbance spectrum of the corresponding cluster compound was measured on a Hitachi U-3900 UV-visible spectrometer using pure 1,2-dichloroethane as a reference (as shown in FIGS. 12, 13 and 14).
Example 13: determination of oxygen release by catalytic water cracking of clusters 6, 8, 9 and 11 on electrode surface
Clusters 6, 8, 9 and 11 were each followed by catalytic water splitting at the electrode surface using the Princeton Applied Research VersaSTAT 3 electrochemical workstation. The test adopts a three-electrode device, wherein the working electrode is an ITO-nano ITO electrode for adsorbing cluster compounds, the counter electrode is a platinum mesh electrode, and the reference electrode is a silver/silver nitrate electrode (the reference liquid is 10mM AgNO) 3 And 100mM LiClO 4 Acetonitrile solution of (a). The electrolyte contains 100mM LiClO 4 And 1.2M Water (H) 2 O) in propylene carbonate. The scanning speed was 10mV/s. Fig. 15, 16, 17 and 18 correspond to catalytic water splitting currents generated by the working electrodes adsorbing clusters 6, 8, 9 and 11, respectively, whereas no significant catalytic current was observed without adsorption of the above clusters.
The clusters were potentiostatic tested. The electrolytic cell is H-type electrolytic cell, and the two chambers are separated by anion exchange membrane. The working electrode and the reference electrode were placed in a chamber containing 100mM LiClO 4 And 1.2M H 2 In a propylene carbonate solution of O, the counter electrode was placed in a solution containing 10mM Li 2 CO 3 /HClO 4 And 100mM LiClO 4 In an aqueous solution (pH =6 to 7). The measured current-time curve is shown in FIG. 19, which shows that the compound of example 9 was preparedThe core structure of the preparation is [ Mn 4 YO 5 ]The cluster compound can be stably catalyzed in the electrolyte for more than 10 hours, and has excellent catalytic stability. At the same time, the process was detected with an Ocean Optics NeoFOX-GT oxygen sensing system with significant oxygen evolution as shown in FIG. 20. The above measurement experiment shows that the core structure is [ Mn ] 4 XO 4 ]And [ Mn 4 XO 5 ]The two clusters have remarkable functions of catalyzing water cracking to release oxygen.
The embodiments of the present invention have been described above by way of example. However, the scope of the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement and the like made by those skilled in the art within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims (10)

1. A rare earth manganese heteronuclear metal cluster, characterized in that the cluster has [ Mn n XO m ]A heteronuclear metal cluster framework core, wherein n is 3 or 4; m is 2,4 or 5; x is selected from rare earth elements.
2. The rare earth heteronuclear manganese metal cluster of claim 1 having one of the following core structures: [ Mn ] 3 XO 2 ]Heteronuclear metal cluster skeleton core, [ Mn ] 4 XO 4 ]Heteronuclear metal cluster framework core and [ Mn ] 4 XO 5 ]The heteronuclear metal cluster skeleton core, and X is selected from rare earth elements.
Preferably, X is selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium.
3. The rare earth manganese heteronuclear metal cluster of claim 1, wherein the chemical formula of the cluster is Mn 3 XO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 The compound has a structure shown as a formula I and contains a rare earth ionX and three Mn ions which pass 2. Mu 3 [ Mn ] bound by O bridges 3 XO 2 ]Heteronuclear metal cluster framework cores;
[Mn 3 XO 2 ]the peripheral ligand of the heteronuclear metal cluster skeleton core is composed of nine carboxylate anions R 1 CO 2 And three neutral carboxylic acid ligands R 1 CO 2 H, wherein the valence states of three Mn ions are +3, +3, +4, respectively, and the whole cluster compound is electrically neutral;
Figure FDA0003225650060000011
wherein X is selected from Sc, Y, la, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb or Lu;
R 1 identical or different, independently of one another, from H or C 1-8 Straight or branched chain alkyl.
Or the chemical formula of the cluster compound is Mn 4 XO 4 (R 1 CO 2 ) 8 (L 1 )(L 2 )(L 3 ) Has a structure shown as a formula II and contains four Mn ions and one rare earth ion X which are connected into [ Mn ] through four mu-O bridges 4 XO 4 ]Heteronuclear metal cluster framework cores;
[Mn 4 XO 4 ]the peripheral ligand of the heteronuclear metal cluster skeleton core is formed by eight carboxylate anions R 1 CO 2 And three ligands L 1 、L 2 And L 3 Providing; wherein the valence states of the four Mn ions are +3, +3, +4, +4;
Figure FDA0003225650060000012
in formula II, rare earth ions X, R 1 Has the meaning as above;
L 1 、L 2 the same or different, each independently selected from carboxylic acid molecules and derivatives thereof, pyridine, imidazole, pyrazine, quinoline, isoquinoline and each thereofOr water molecules, alcohol molecules, ethers, ketones, nitriles, esters, amides and their respective derivatives, or L 1 And L 2 Linked as a bidentate chelating ligand;
L 3 selected from carboxylic acid molecules and derivatives thereof, pyridine, imidazole, pyrazine, quinoline, isoquinoline and respective derivatives thereof, or water molecules, alcohol molecules, ethers, ketones, nitriles, esters, amides and respective derivatives thereof.
Or the chemical formula of the cluster compound is Mn 4 XO 5 H(R 1 CO 2 ) 8 (L 4 )(L 5 ) Has a structure shown in formula III, and contains four Mn ions and one rare earth ion which are connected into [ Mn ] through five mu-O 4 XO 5 ]Heteronuclear metal cluster framework cores; [ Mn ] 4 XO 5 ]The peripheral ligand of the heteronuclear metal cluster skeleton core is formed by eight carboxylate anions R 1 CO 2 And two ligands L 4 And L 5 Providing; [ Mn ] 4 XO 5 ]The heteronuclear metal cluster skeleton core has one mu 2 -an O-bridge; the valence states of the four manganese ions are +3, +3, +4, +4;
Figure FDA0003225650060000021
in formula III, rare earth ions X, R 1 Has the meaning as above; l is 4 And L 5 Identical or different, independently of one another, from the group consisting of carboxylic acid molecules and derivatives thereof, pyridine, imidazole, pyrazine, quinoline, isoquinoline and respective derivatives thereof, or water molecules, alcohol molecules, ethers, ketones, nitriles, esters, amides and respective derivatives thereof, or L 4 And L 5 The linkage is a bidentate chelating ligand.
4. The rare earth manganese heteronuclear metal cluster compound according to claim 3, wherein the cluster compound having the structure shown in formula I is selected from any one of the following cluster compounds 1 to 5:
cluster compound 1 of the formula Mn 3 YO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 Wherein R is 1 = tert-butyl;
cluster 1 is a single crystal; the structure is shown as formula I-1:
Figure FDA0003225650060000022
the single crystal belongs to a triclinic system, the space group is P-1, and the unit cell parameter is
Figure FDA0003225650060000023
Figure FDA0003225650060000024
α =77.526 (3) °, β =87.004 (2) °, γ =65.818 (3) °, Z =2, and has a volume of
Figure FDA0003225650060000025
Cluster 2 of the formula Mn 3 LaO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 Wherein R is 1 = tert-butyl;
cluster 2 is a single crystal; the structure is shown as formula I-2:
Figure FDA0003225650060000026
the single crystal belongs to a monoclinic system, and the space group is P2 1 N, unit cell parameter of
Figure FDA0003225650060000027
Figure FDA0003225650060000028
α =90 °, β =107.516 (4) °, γ =90 °, Z =4, and volume
Figure FDA0003225650060000029
Cluster 3 of the formula Mn 3 GdO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 Wherein R is 1 = tert-butyl;
cluster 3 is a single crystal; the structure is shown as formula I-3:
Figure FDA0003225650060000031
the single crystal belongs to a triclinic system, the space group is P-1, and the unit cell parameter is
Figure FDA0003225650060000032
Figure FDA0003225650060000033
α =77.898 (2) °, β =87.087 (2) °, γ =65.755 (2) °, Z =2, and has a volume of
Figure FDA0003225650060000034
Cluster compound 4 of the formula Mn 3 DyO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 Wherein R is 1 = tert-butyl;
cluster 4 is a single crystal; the structure is shown in formula I-4:
Figure FDA0003225650060000035
the single crystal belongs to a triclinic system, the space group is P-1, and the unit cell parameter is
Figure FDA0003225650060000036
Figure FDA0003225650060000037
α =77.790 (2) °, β =86.995 (2) °, γ =65.678 (2) °, Z =2, and has a volume of
Figure FDA0003225650060000038
Cluster 5 of the formula Mn 3 LuO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 Wherein R is 1 = tert-butyl;
cluster 5 is a single crystal; the structure is shown as formula I-5:
Figure FDA0003225650060000039
the single crystal belongs to a triclinic system, the space group is P-1, and the unit cell parameter is
Figure FDA00032256500600000310
Figure FDA00032256500600000311
α =77.450 (3) °, β =87.291 (3) °, γ =65.954 (3) °, Z =2, and has a volume of
Figure FDA00032256500600000312
5. The rare earth manganese heteronuclear metal cluster according to claim 3, wherein the cluster having the structure represented by formula II is selected from any one of the following clusters 6 to 8:
cluster compound 6 of the formula Mn 4 YO 4 (R 1 CO 2 ) 8 (L 1 )(L 2 )(L 3 ) Wherein R is 1 = tert-butyl, L 1 And L 2 After ligation is pivalate (e.g., trimethylacetate, i.e., R in formula II-1) 2 Is tert-butyl), L 3 = isoquinoline;
the cluster compound 6 is a single crystal; the structure is shown as formula II-1:
Figure FDA00032256500600000313
the single crystal belongs to a monoclinic system, and the space group is P2 1 N, unit cell parameter of
Figure FDA00032256500600000314
Figure FDA0003225650060000041
α =90.00 °, β =101.6590 (10) °, γ =90.00 °, Z =4, and volume
Figure FDA0003225650060000042
Cluster compound 7 of the formula Mn 4 GdO 4 (R 1 CO 2 ) 8 (L 1 )(L 2 )(L 3 ) Wherein R is 1 = tert-butyl, L 1 And L 2 After linkage is pivalate, i.e. R in formula II-2 2 Is tert-butyl, L 3 = isoquinoline;
the cluster compound 7 is a single crystal; the structure is shown as formula II-2:
Figure FDA0003225650060000043
the single crystal belongs to a monoclinic system, and the space group is P2 1 N, unit cell parameter of
Figure FDA0003225650060000044
Figure FDA0003225650060000045
α =90.00 °, β =101.799 (2) °, γ =90.00 °, Z =4, and volume
Figure FDA0003225650060000046
Cluster 8 of the formula Mn 4 LuO 4 (R 1 CO 2 ) 8 (L 1 )(L 2 )(L 3 ) Wherein R is 1 = tert-butyl, L 1 And L 2 After linkage is pivalate, i.e. R in formula II-3 2 Is tert-butyl, L 3 = isoquinoline;
the cluster 8 is a single crystal; the structure is shown as formula II-3:
Figure FDA0003225650060000047
the single crystal belongs to a monoclinic system, and the space group is P2 1 N, unit cell parameter of
Figure FDA0003225650060000048
Figure FDA0003225650060000049
α =90.00 °, β =101.7670 (10) °, γ =90.00 °, Z =4, and volume
Figure FDA00032256500600000410
6. The rare earth manganese heteronuclear metal cluster according to claim 3, wherein the cluster having the structure represented by formula III is selected from any one of the following clusters 9 to 11:
cluster 9 of the formula Mn 4 YO 5 H(RCO 2 ) 8 (L 4 )(L 5 ) Wherein R is 1 = tert-butyl; l is a radical of an alcohol 4 、L 5 Are both N, N-dimethylacetamide;
the cluster compound 9 is a single crystal; the structure is shown as formula III-1:
Figure FDA00032256500600000411
the single crystal belongs to an orthorhombic system, the space group is Pbca, and the unit cell parameter is
Figure FDA00032256500600000412
Figure FDA00032256500600000413
α =90 °, β =90 °, γ =90 °, Z =8, and a volume of
Figure FDA00032256500600000414
Cluster 10 of the formula Mn 4 DyO 5 H(RCO 2 ) 8 (L 4 )(L 5 ) Wherein R is 1 = tert-butyl; l is 4 、L 5 Are both N, N-dimethylacetamide;
the cluster compound 10 is a single crystal; the structure is shown as formula III-2:
Figure FDA0003225650060000051
the single crystal belongs to an orthorhombic system, the space group is Pbca, and the unit cell parameter is
Figure FDA0003225650060000052
Figure FDA0003225650060000053
α =90 °, β =90 °, γ =90 °, Z =8, and a volume of
Figure FDA0003225650060000054
Cluster 11 of the formula Mn 4 LuO 5 H(RCO 2 ) 8 (L 4 )(L 5 ) Wherein R is 1 = tert-butyl; l is 4 、L 5 Are both N, N-dimethylacetamide;
the cluster compound 11 is a single crystal; the structure is shown as formula III-3:
Figure FDA0003225650060000055
the single crystal belongs to an orthorhombic system, the space group is Pbca, and the unit cell parameter is
Figure FDA0003225650060000056
Figure FDA0003225650060000057
α =90 °, β =90 °, γ =90 °, Z =8, and a volume of
Figure FDA0003225650060000058
7. The method of preparing a rare earth manganese heteronuclear metal cluster according to any of claims 1 to 6, comprising the steps of: and (2) reacting the permanganate anion type oxidant, the rare earth salt and the ligand, optionally adding water or a divalent manganese salt, in a solution to prepare the cluster compound.
8. The method of claim 7, wherein the chemical formula of the rare earth manganese heteronuclear metal cluster compound is Mn 3 XO 2 (R 1 CO 2 ) 9 (R 1 CO 2 H) 3 The preparation method of the cluster compound comprises the following steps: reacting an organic carboxylic acid R 1 COOH, permanganate anion type oxidant, rare earth salt, water or bivalent manganese salt are optionally added, and the cluster compound is prepared by reaction in acetonitrile solution.
Or the chemical formula of the structure shown in the formula II is Mn 4 XO 4 (R 1 CO 2 ) 8 (L 1 )(L 2 )(L 3 ) The preparation method of the cluster compound comprises the following steps:
(1) Reacting an organic carboxylic acid R 1 COOH, permanganate radical anion type oxidant, divalent manganese salt and rare earth salt react in acetonitrile solution to prepare an intermediate;
(2) The intermediate in the step (1) is reacted with a ligand L 3 Reaction, optionally with ligand L 1 And/or L 2 Reacting to obtain Mn with a chemical formula shown as a formula II 4 XO 4 (R 1 CO 2 ) 8 (L 1 )(L 2 )(L 3 ) The cluster compound of (1);
or the chemical formula with the structure shown in the formula III is Mn 4 XO 5 H(R 1 CO 2 ) 8 (L 4 )(L 5 ) The preparation method of the cluster compound comprises the following steps: dissolving cluster compound with structure shown in formula II in halogenated hydrocarbon and/or ester solvent, adding water, optionally adding or not adding ligand L 4 And a ligand L 5 And reacting to obtain the cluster compound with the structure shown in III.
9. A biomimetic water splitting catalyst, comprising the cluster compound of any of claims 1-6.
10. Use of the biomimetic water splitting catalyst of claim 9, wherein the catalyst is used to catalyze splitting of water. Preferably, the catalytic process is carried out at the surface of an electrode, or in the presence of an oxidant.
CN202110970907.0A 2021-08-23 2021-08-23 Bionic water cracking catalyst containing rare earth ions and preparation method and application thereof Pending CN115710292A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110970907.0A CN115710292A (en) 2021-08-23 2021-08-23 Bionic water cracking catalyst containing rare earth ions and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110970907.0A CN115710292A (en) 2021-08-23 2021-08-23 Bionic water cracking catalyst containing rare earth ions and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN115710292A true CN115710292A (en) 2023-02-24

Family

ID=85230408

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110970907.0A Pending CN115710292A (en) 2021-08-23 2021-08-23 Bionic water cracking catalyst containing rare earth ions and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115710292A (en)

Similar Documents

Publication Publication Date Title
Yin et al. A noble-metal-free photocatalytic hydrogen production system based on cobalt (III) complex and eosin Y-sensitized TiO 2
Harman et al. Isostructural. eta. 2-dihydrogen complexes [Os (NH3) 5 (H2)] n+ (n= 2, 3) and the hydrogenation of acetone
EP3255053B1 (en) METHOD OF PREPARING WATER-CRACKING CATALYST HAVING Mn4CaO4 AS CORE STRUCTURE AND APPLICATION THEREOF
Ishida et al. Ligand effects of ruthenium 2, 2′-bipyridine and 1, 10-phenanthroline complexes on the electrochemical reduction of CO2
CN112592361B (en) Fluoroboropyrrole functionalized metal organic framework material and preparation method and application thereof
CN114195827B (en) Carboxyl substituted ruthenium complex and preparation method and application thereof
CN107175133A (en) A kind of silicon dioxide carried copper dipyridyl catalyst and preparation method thereof
EP3705484B1 (en) Cluster compound containing mn3sro4 and mn4sro4 core structures, preparation method thereof, and application for same
CN114716459A (en) Carboxyl substituted ruthenium complex, preparation method and application thereof
CN115710292A (en) Bionic water cracking catalyst containing rare earth ions and preparation method and application thereof
CN104148112B (en) Catalytic oxygen production system containing duplex pyridine ruthenium (II) complex, preparation method of duplex pyridine ruthenium (II) complex and oxygen production method
JP3366566B2 (en) Manganese complex catalyst for oxygen reduction
CN102558555B (en) High-temperature-resistant ultraviolet absorbent containing polyfluorene triazole and preparation method thereof
Shatskiy et al. Catalyst–solvent interactions in a dinuclear Ru-based water oxidation catalyst
EP4261216A1 (en) Pyridine pyrrole ruthenium complex, preparation method therefor and application thereof as catalyst for preparing hydrazine by electrocatalytic ammonia oxidation
WO2023023898A1 (en) Rare earth ion-containing bionic water cracking catalyst, and preparation method therefor and use thereof
CN109748939B (en) Containing [ Mn3SrO4]And [ Mn4SrO4]Cluster compound with core structure and preparation method and application thereof
US6316653B1 (en) Mn4O4-cubane type catalysts
US20130277229A1 (en) Novel metal complex catalysts and uses thereof
Yang et al. Structural evolution of the Ru-bms complex to the real water oxidation catalyst of Ru-bda: the bite angle matters
Zhou et al. A Pd 4 L 2 cage containing Brønsted-base active sites for the one-pot photooxidation/Knoevenagel condensation reaction
Yagodin et al. Carboxyphenyl Substituted Pyrazinoporphyrazines–Promising Linkers for Metal-Organic Frameworks
CN114685535B (en) Carboxyl substituted ruthenium complex and preparation method and application thereof
Yamamoto et al. Manganese-cerium porphyrin tri-nuclear complex as a catalyst for water oxidation
Vo et al. Intercepting a Transient Pyridine N-Oxide Fe (III) Species in Catalytic Oxygen Atom Transfer Reaction

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination