CN117899942A - High-nuclear manganese oxide cluster crystal material and preparation method and application thereof - Google Patents
High-nuclear manganese oxide cluster crystal material and preparation method and application thereof Download PDFInfo
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 52
- 239000013078 crystal Substances 0.000 title claims abstract description 33
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- 229910003176 Mn-O Inorganic materials 0.000 claims description 9
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- 125000004429 atom Chemical group 0.000 claims description 6
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Abstract
The invention belongs to the technical field of preparation of nano-cluster crystal materials, and relates to a high-nuclear manganese oxide cluster crystal material, a preparation method and application thereof. The chemical molecular formula of the high-nuclear manganese oxide cluster crystal material is Mn II 8MnIII 10O10(OOCMe)12(OMe)14(py)2 and is named Mn 18 -Ac. The Mn 18 -Ac has novel structure and higher stability, and the mixed valence state of Mn II and Mn III exists in the crystal structure, so that the cluster crystal material is suitable for oxidation-reduction reaction and advanced oxidative degradation application of the pollutant tetracycline.
Description
Technical Field
The invention belongs to the technical field of preparation of nano-cluster crystal materials, and relates to a high-nuclear manganese oxide cluster crystal material, a preparation method and application thereof.
Background
In recent years, new pollutants such as volatile organic compounds, endocrine disruptors, microplastic, antibiotics and the like are attracting attention by means of neurotoxicity, immunotoxicity, reproductive and developmental toxicity, carcinogenicity, teratogenicity and the like, and such improper treatment is extremely liable to cause serious influence on ecological environment and human health. Currently, adsorption enrichment, biodegradation, advanced oxidation, and other processes are applied to new contaminant abatement. It should be noted that the biodegradation process has severe requirements on treatment conditions and is selective to pollutants; the adsorption enrichment process is limited by unsatisfactory efficiency, easy formation of secondary pollution or solid waste, and the like. Advanced oxidation technology generates free radicals by activating oxygen species, can realize efficient degradation of pollutants, and is the most widely used purification technology at present.
Various free radicals including hydroxyl free radicals, sulfate free radicals, superoxide free radicals, singlet oxygen and the like can be generated through advanced oxidation processes, particularly activated Peroxymonosulfate (PMS), and the active peroxymonosulfate has good degradation effect on various pollutants. Currently, noble metal catalysts and transition metal catalysts have been primarily applied to PMS activation and contaminant advanced oxidation. In view of catalyst cost and degradation efficiency, development of a high-efficiency and low-cost novel transition metal catalytic material is important for practical application.
The manganese element has the characteristics of rich reserves, wide valence state distribution and the like, and is one of the star elements in the catalysis field. In addition, metal clusters are ideal platforms for metal center valence state regulation, charge regulation and redox performance regulation by virtue of unique quantum size effects, and have attracted great attention in recent years. It is noted that due to the extremely high surface energy, such materials are generally less stable and creating new structures is more challenging. The invention designs and synthesizes a novel high-nuclear manganese oxide cluster from the control of synthesis conditions, wherein the mixed valence state and unique coordination environment of Mn II and Mn III endow the cluster with excellent stability and catalytic performance. Can efficiently activate PMS to realize Tetracycline (TC) degradation, thus being used as a practical catalyst for advanced oxidative degradation of new pollutants. The invention provides a generalization way for developing a novel high-nuclear manganese oxide cluster material and developing a high-grade oxidation process catalyst with industrial application potential.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a high-nuclear manganese oxide cluster crystal material, and a preparation method and application thereof.
A first object of the present invention is to provide a high nuclear manganese oxide cluster crystal material having a chemical formula of Mn II 8MnIII 10O10(OOCMe)12(OMe)14(py)2, designated Mn 18 -Ac.
On the basis of the scheme, further, from the angle of framework connection construction, the crystal structure of Mn 18 -Ac belongs to a triclinic system, the space group is P-1, and the unit cell parameters are as follows: a= 10.4312 (5) a, b= 13.1605 (6) a, c= 16.2948 (8) a, α= 106.181 (3) °, β= 99.194 (4) °, γ= 90.133 (4) °.
Based on the scheme, further, the crystal structure of the Mn 18 -Ac cluster consists of 18 crystallographically independent Mn atoms and is divided into an inner core and an outer core through a- [ Mn-O-Mn-O ] -framework, wherein bridging oxygen is O 2- (inner core) or CH 3O- (outer core); the inner core of the cluster consists of 6 [ Mn 4O4 ] cubes, O 2- ions and oxygen atoms from methoxy (CH 3O-) are also involved in the construction of the- [ Mn-O-Mn-O ] -structural framework, the bonding form is μ 2 or μ 3 bridge mode; the outer core is formed by assembling and growing Mn ions and ligands, neutral pyridine and methanol molecules serve as sigma donor ligands and are connected to Mn sites at the edge; acetate bonds to metal in a tridentate bridging mode and a chelate/bridging coexistence mode; the Mn centers form a distorted coordination environment to maintain the inherent ligand geometry.
Based on the scheme, further, mn ions in the Mn 18 -Ac cluster exist in divalent and trivalent states at the same time, and specifically comprise 8 Mn II and 10 Mn III; divalent Mn ions exhibit longer average Mn-O bond lengths than trivalent Mn ions, mn II -O average bond lengths ranging from 2.179 to 2.250A, mn III -O average bond lengths of 2.046A;
The ions occupying the highest MO sites in the Mn 18 -Ac structure are localized on the outer Mn II ions, which are sequestered by the acetic acid ligand, while the unoccupied lowest MO is contributed by the inner Mn III ions. The Mn central oxidation state and the unique coordination environment endow the manganese oxide cluster with excellent stability and redox characteristics, so that the material is suitable for activating PMS for advanced oxidative degradation of new pollutants.
The invention also aims to provide a preparation method of the high-nuclear manganese oxide cluster crystal material, which comprises the following steps:
Under a closed condition, the organic ligand pyridine (py), methanol and manganese acetate (Mn (OOCCH 3)3∙2H2 O) are dissolved in acetonitrile, triethylamine (Et 3 N) is added to adjust the pH value of the solution, and brown crystals are obtained through coordination reaction and low-temperature crystallization.
Based on the scheme, further, the addition proportion of the manganese acetate to the organic ligand py is 0.1mmol of manganese acetate, which corresponds to 0.2-0.375mL of py; the addition ratio of the manganese acetate to the triethylamine Et 3 N is 0.1mmol of manganese acetate, which corresponds to 0.1-0.2mL of triethylamine Et 3 N; the manganese acetate and methanol are added in a ratio of 0.1mmol of manganese acetate to 1-15mL of methanol.
Based on the scheme, the temperature of the coordination reaction is 20-100 ℃, the reaction time of the coordination reaction is 2-24 hours, the low-temperature crystallization temperature is-10-5 ℃, and the low-temperature crystallization time is 7-14 days.
The invention also aims to provide an application of the high-nuclear manganese oxide cluster crystal material in degrading tetracycline advanced oxidative degradation.
The beneficial technical effects of the invention are as follows: the high-nuclear manganese oxide cluster crystal material has novel structure and higher stability, and the mixed valence state of Mn II and Mn III exists in the crystal structure, so that the cluster crystal material is suitable for oxidation-reduction reaction and pollutant advanced oxidative degradation application.
Drawings
FIG. 1 is a diagram of the metal core configuration of Mn 18 -Ac (Mn II, purple; mn III, pink; O, red; N, blue; C, gray);
FIG. 2 is a metal center coordination structure of Mn 18 -Ac;
FIG. 3 is a schematic diagram of the outer core assembly structure of Mn 18 -Ac;
FIG. 4 is a diagram showing coordination patterns of exonuclear metals and organic ligands in Mn 18 -Ac;
FIG. 5 is a schematic diagram of the assembly of units of cubic [ M 4O4 ] in Mn 18 -Ac;
FIG. 6 is a graph showing bond lengths of Mn-O ions in Mn 18 -Ac;
FIG. 7 is a front rail plot of Mn 18 -Ac;
FIG. 8 is a graph of the magnetic properties of Mn 18 -Ac;
FIG. 9 is an X-ray photoelectron spectrum of a metal in Mn 18 -Ac;
FIG. 10 is a graph of the near-edge absorption spectrum of metals in Mn 18 -Ac;
FIG. 11 is a graph of the first-order derivative X-ray near-edge absorption spectrum of Mn 18 -Ac;
FIG. 12 is a graph of Mn 18 -Ac versus tetracycline adsorption performance;
FIG. 13 is a graph of Mn 18 -Ac catalyzed tetracycline advanced oxidative degradation activity;
FIG. 14 is a graph fitted with Mn 18 -Ac catalyzed high-level oxidative degradation kinetics of tetracycline;
FIG. 15 is a graph comparing Mn 18 -Ac with the advanced oxidative degradation rate of manganese oxide catalyzed tetracyclines.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
13.5Mg (0.05 mmol) of manganese (III) acetate dihydrate (Mn (OOCCH 3)3∙2H2 O) was suspended in acetonitrile, to which suspension 0.1mL of pyridine (py) and 0.05mL of triethylamine (Et 3 N) were added, which was heated and stirred continuously, the heating temperature was 20 ℃ C. Followed by the addition of 1mL of methanol and the reaction was continued for 6 hours to give a brown clear solution and a little brown precipitate.
Example 2
27Mg (0.1 mmol) of manganese (III) acetate dihydrate (Mn (OOCCH 3)3∙2H2 O) was suspended in acetonitrile, to which suspension 0.3mL of pyridine (py) and 0.1mL of triethylamine (Et 3 N) were added, which was heated and stirred continuously, at a temperature of 100 ℃ C. Then 1mL of methanol was added and the reaction was continued for 10 hours to give a brown clear solution and a little brown precipitate.
Example 3
54Mg (0.2 mmol) of manganese (III) acetate dihydrate (Mn (OOCCH 3)3∙2H2 O) was suspended in acetonitrile, to which suspension 0.5mL of pyridine (py) and 0.2mL of triethylamine (Et 3 N) were added, which was heated and stirred continuously, the heating temperature was 60 ℃ C. Followed by 5mL of methanol and further reaction was continued for 2 hours to give a brown clear solution and a little brown precipitate.
Example 4
108Mg (0.4 mmol) of manganese (III) acetate dihydrate (Mn (OOCCH 3)3∙2H2 O) was suspended in acetonitrile, to which suspension 1.5mL of pyridine (py) and 0.8mL of triethylamine (Et 3 N) were added, which was heated and stirred continuously at 50 ℃ C. Followed by 15mL of methanol and continued reaction for 24h to give a brown clear solution and a little brown precipitate.
(1) Characterization of the crystal structure:
The appropriate size single crystals were selected under a microscope and Mn 18 -Ac data were collected on a BrukerD8VENTUREX ray diffractometer, with a photon 100CMOS detector equipped with a copper target. Micro focus source I [ mu ] SX tube (λ=1.5406 a) with t=160k. Data reduction and integration was performed using the Bruker package saint (version 8.38A) and absorption effect correction was performed using the empirical method implemented in SADABS (version 2016/2). The structure is obtained through SHELXT and refined through OLEX graphical interface using Brukershelxtl (version 2018/3) software package through full matrix least squares program. The crystallographic data are shown in table 1.
TABLE 1 crystallographic data of metal-organic framework materials
。
FIG. 1 is a diagram of the metal core configuration of Mn 18 -Ac, showing that: mn 18 -Ac is assembled from Mn atoms by coordination with bridging oxygen (O 2-) or pyridine, an organic ligand.
FIG. 2 is a metal center coordination structure of Mn 18 -Ac, showing that: the Mn 18 -Ac structure is composed of core made up of Mn atoms through [ -Mn-O-Mn ], and core made up of Mn atoms and bridging oxygen (O 2-) or organic ligand through [ Mn-O ] or [ Mn-N ].
FIG. 3 is a schematic diagram of the outer core assembly structure of Mn 18 -Ac, showing that: the Mn 18 -Ac structural core consists of 6 cube units [ Mn 4O4 ] with almost identical geometries.
FIG. 4 is a graph showing the coordination pattern of the exo-core metal and the organic ligand in Mn 18 -Ac, showing that: acetate and pyridine in the outer core of the Mn 18 -Ac structure have different coordination modes with Mn, wherein acetate ligands are bridged by three branches and chelate/bridge, and MeOH molecules are used as sigma-donor ligands to be attached to Mn atoms at the corners.
FIG. 5 is a schematic diagram of the assembly of units of cubic [ M 4O4 ] in Mn 18 -Ac, showing: the assembly of Mn 18 -Ac structural cores [ Mn 4O4 ] units was grown in two steps starting from the central cube 1. First, the [ Mn 4O4 ] cube (cube 2) grows along the +z direction of 1, forming an overall cube geometry that stacks the two cubes along the z-axis. Next, the two cubes 1 and 2 continue to replicate and extend in different directions. Wherein cube 1 replicates cubes 5 and 6 in its +x and-y directions and cubes 3 and 4 in its-x and +y directions, ultimately forming a six-cube assembled structure.
FIG. 6 is a graph of bond lengths of Mn-O ions in Mn 18 -Ac, showing that: the bond length of Mn ions in the Mn 18 -Ac structure ranges from 2.046 to 2.250A, where Mn II -O bond length is slightly greater than Mn III -O bond length.
FIG. 7 is a front rail plot of Mn 18 -Ac showing: the ions occupying the highest MO sites in the Mn 18 -Ac structure are localized on the outer Mn II ions, which are sequestered by the acetic acid ligand, while the unoccupied lowest MO is contributed by the inner Mn III ions.
(2) Physical and chemical property characterization:
FIG. 8 is a graph of the magnetic properties of Mn 18 -Ac, showing that: mn 18 -Ac has a maximum magnetic moment of 120emu at a temperature range of 5-300K and a X M T value of 39.05cm 3·K·mol-1. After cooling, the χ M T value remained unchanged, dropping sharply to 19.54cm 3·K·mol-1 around 40K, indicating a higher ferromagnetic interaction between Mn ions in the clusters.
FIG. 9 is an X-ray photoelectron spectrum of a metal in Mn 18 -Ac showing that: the Mn element in the Mn 18 -Ac structure mainly exists in an oxidation state, and the Mn element mainly has two valence states of Mn II and Mn III through peak-splitting fitting and comparison.
FIG. 10 is an X-ray near-edge absorption spectrum of a metal in Mn 18 -Ac, showing that: mn 18 -Ac shows a typical MnK edge characteristic, attributable to electron transfer from 1s to 4p orbitals, the curve lies between the MnO and Mn 2O3 reference samples, which coincides with the mixed valency of the manganese ions in the clusters.
FIG. 11 is a first order derivative X-ray near side absorption spectrum of Mn 18 -Ac showing: the manganese K edge energies of Mn foil, mnO, mn 2O3 and MnO 2 are 6539.0, 6544.5, 6553.0 and 6558.0eV respectively, and the manganese K edge energy of Mn 18 -Ac structure is 6548.0eV, which is between MnO and Mn 2O3 standard.
(3) Characterization of advanced oxidative degradation properties of tetracyclines:
FIG. 12 is a graph of Mn 18 -Ac versus tetracycline adsorption performance, showing that: mn 18 -Ac has only weak adsorption performance on tetracycline, and the material cannot be directly used for adsorption removal of the tetracycline.
FIG. 13 is a graph of Mn 18 -Ac catalyzed tetracycline advanced oxidative degradation activity, showing that: mn 18 -Ac can efficiently activate Peroxymonosulfate (PMS) to degrade tetracycline, and the reaction time is 40 minutes to realize 95.2% pollutant degradation, and the activity is obviously higher than that of a manganese oxide catalyst.
FIG. 14 is a graph fitted with Mn 18 -Ac catalyzed high-level oxidative degradation kinetics of tetracyclines, showing that: mn 18 -Ac catalyzes the advanced oxidation of tetracyclines following pseudo first order kinetics, with a rate constant (k) of 2.18X10 -3s-1 by linear fitting.
FIG. 15 is a graph comparing Mn 18 -Ac with the advanced oxidative degradation rate of manganese oxide catalyzed tetracyclines, showing that: mn 18 -Ac showed a faster reaction rate in the higher oxidation of tetracycline, with a rate constant (k) 12.5 times that of the commercial manganese oxide catalyst.
(4) Analysis of advanced oxidation mechanism of tetracycline:
The following mechanism analysis of Mn 18 -Ac activated PMS degradation of tetracyclines according to the present invention. Under the coexistence condition of Mn 18 -Ac and PMS, metal sites on clusters generate a large amount of oxygen-containing free radicals through oxidation-reduction reaction with PMS, and the molecular structure of the tetracycline can be damaged by virtue of strong oxidation of the free radicals, so that the tetracycline is gradually changed into small molecules until CO 2, and finally complete degradation of the tetracycline is realized.
Claims (8)
1. A high nuclear manganese oxide cluster crystal material, characterized in that: the chemical molecular formula of the high-nuclear manganese oxide cluster crystal material is Mn II 8MnIII 10O10(OOCMe)12(OMe)14(py)2 and is named Mn 18 -Ac.
2. The high nuclear manganese oxide cluster crystal material according to claim 1, characterized in that: from the angle of framework connection construction, the crystal structure of Mn 18 -Ac belongs to a triclinic system, the space group is P-1, and the unit cell parameters are as follows: a= 10.4312 (5) a, b= 13.1605 (6) a, c= 16.2948 (8) a, α= 106.181 (3) °, β= 99.194 (4) °, γ= 90.133 (4) °.
3. The high nuclear manganese oxide cluster crystal material according to claim 2, characterized in that: the crystal structure of the Mn 18 -Ac cluster consists of 18 crystallographically independent Mn atoms which are separated into an inner core and an outer core through a- [ Mn-O-Mn-O ] -framework, wherein bridging oxygen is O 2- (inner core) or CH 3O- (outer core); the inner core of the cluster consists of 6 [ Mn 4O4 ] cubes, O 2- ions and oxygen atoms from methoxy (CH 3O-) are also involved in the construction of the- [ Mn-O-Mn-O ] -structural framework, the bonding form is μ 2 or μ 3 bridge mode; the outer core is formed by assembling and growing Mn ions and ligands, neutral pyridine and methanol molecules serve as sigma donor ligands and are connected to Mn sites at the edge; acetate bonds to metal in a tridentate bridging mode and a chelate/bridging coexistence mode; the Mn centers form a distorted coordination environment to maintain the inherent ligand geometry.
4. A high nuclear manganese oxide cluster crystal material according to claim 3, characterized in that: the Mn ions in the Mn 18 -Ac cluster have divalent and trivalent simultaneously, and specifically comprise 8 Mn II and 10 Mn III; divalent Mn ions exhibit longer average Mn-O bond lengths than trivalent Mn ions, mn II -O average bond lengths ranging from 2.179 to 2.250A, mn III -O average bond lengths of 2.046A;
the ions occupying the highest MO sites in the Mn 18 -Ac structure are localized on the outer Mn II ions, which are sequestered by the acetic acid ligand, while the unoccupied lowest MO is contributed by the inner Mn III ions.
5. A method for preparing the high nuclear manganese oxide cluster crystal material according to any one of claims 1 to 4, wherein: the method comprises the following steps:
Under a closed condition, the organic ligand pyridine (py), methanol and manganese acetate (Mn (OOCCH 3)3∙2H2 O) are dissolved in acetonitrile, triethylamine (Et 3 N) is added to adjust the pH value of the solution, and brown crystals are obtained through coordination reaction and low-temperature crystallization.
6. The method for preparing the high nuclear manganese oxide cluster crystal material according to claim 5, wherein the method comprises the following steps: manganese acetate with the addition amount ratio of 0.1mmol of manganese acetate to organic ligand py corresponds to 0.2-0.375mL of py; the addition ratio of the manganese acetate to the triethylamine Et 3 N is 0.1mmol of manganese acetate, which corresponds to 0.1-0.2mL of triethylamine Et 3 N; the manganese acetate and methanol are added in a ratio of 0.1mmol of manganese acetate to 1-15mL of methanol.
7. The method for preparing the high nuclear manganese oxide cluster crystal material according to claim 5, wherein the method comprises the following steps: the coordination reaction temperature is 20-100 ℃, the reaction time of the coordination reaction is 2-24 hours, the low-temperature crystallization temperature is-10-5 ℃, and the low-temperature crystallization time is 7-14 days.
8. Use of the high nuclear manganese oxide cluster crystal material according to any one of claims 1-4 in advanced oxidative degradation of tetracycline, a new contaminant of water.
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