Method for regulating and controlling crystal morphology of multi-metal-based prussian blue analogue by utilizing ligand competitive coordination
Through ligand competition coordination, the crystal morphology of polymetallic Prussian blue analogs was regulated, and the morphology evolution from epitaxial growth to core-shell structure and then to hollow structure was achieved. High-efficiency composite materials suitable for energy catalysis.
Patent Information
- Application Number
- CN202411178405.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-08-27
- Publication Date
- 2024-12-24
AI Technical Summary
The prior art is difficult to achieve precise regulation of the morphology of multifunctional Prussian blue analog materials, which affects its catalytic efficiency and performance.
The crystal morphology of polymetallic Prussian blue analogues is regulated through ligand competition coordination, and the coordination reaction is carried out using manganese acetate, surfactant, cobalt potassium cyanide and potassium ferrocyanide to control the reaction time to obtain different morphology The evolution of polymetallic bisoprustic blue analog crystals from epitaxial growth to core-shell structures to hollow structures.
It realizes precise morphology regulation, obtains high-purity, good crystallinity and high yield composite materials, which are suitable for energy catalysis and other fields, and are low-cost and simple to operate.
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Figure CN119176571A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of porous micro-nano composite material synthesis, and in particular relates to a method for regulating the crystal morphology of multi-metal-based Prussian blue analogs by utilizing ligand competitive coordination. Background Art
[0002] Prussian blue analogue (PBA) is a kind of metal organic framework (MOF) material with a three-dimensional open framework and high stability. PBA is easy to synthesize and inexpensive. It is composed of metal ions coordinated with cyanide ligands. Using different metal ions, a series of PBAs with similar chemical composition, diverse shapes and uniform sizes can be obtained. In addition, because the crystal structure of Prussian blue compounds has an open framework structure and large pores, it can store Li + 、Na + , K + Prussian blue compounds are widely studied as electrode materials because they can absorb alkali metal ions and have short ion diffusion paths. In addition, as a typical nanomaterial, PBA has the advantages of nanoscale size, simple preparation, and adjustable morphology, and can be applied to electrochemical energy storage, catalysis, adsorption and other fields.
[0003] Multifunctional PBA is used as a precursor due to its tunable nanostructure and rich morphology. Using a variety of strategies to control the morphology of PBA, complex morphologies such as core-shell structure and hollow structure can be designed. The morphology directly affects the specific surface area, exposed crystal faces and surface defects of the material, which in turn affects the catalytic efficiency and performance. Therefore, precise control of the morphology of multifunctional PBA materials can significantly improve the performance and application potential of multifunctional PBA catalysts.
[0004] However, many current studies still cannot achieve the precise control and design of multifunctional PBA morphology. Summary of the invention
[0005] The purpose of the present invention is to provide a method for regulating the crystal morphology of a multi-metallic Prussian blue analogue by using ligand competitive coordination. The morphology of the composite material obtained by the preparation method provided by the present invention realizes the evolution from epitaxial growth to a core-shell structure and then to a hollow structure, and the production cost is low and the operation is simple. The prepared complex multi-morphology composite material can be widely used in fields such as energy catalysis.
[0006] In order to achieve the above object, the present invention provides the following technical solutions:
[0007] The present invention provides a method for regulating the crystal morphology of a multi-metal-based Prussian blue analog by using ligand competitive coordination, comprising the following steps:
[0008] Manganese acetate, a surfactant, potassium cobalt cyanide and water are mixed to perform a first coordination reaction to obtain a MnCoPBA solution;
[0009] The MnCoPBA solution and potassium ferrocyanide are mixed to carry out a second coordination reaction, and the duration of the second coordination reaction is controlled to obtain multi-metallic Prussian blue analog crystals with different morphologies; the multi-metallic Prussian blue analog crystals include MnFeCoPBA crystals.
[0010] Preferably, the second coordination reaction time is 30 minutes, the multi-metallic Prussian blue analogue includes MnCoPBA crystals and MnFeCoPBA crystals, and the morphology of the multi-metallic Prussian blue analogue is that the MnFeCoPBA crystals are epitaxially grown on a partial area of the surface of the MnCoPBA crystals.
[0011] Preferably, the time of the second coordination reaction is 2 hours, the multi-metal-based Prussian blue analogue includes MnCoPBA crystals and MnFeCoPBA crystals, and the morphology of the multi-metal-based Prussian blue analogue is a core-shell structure, the shell layer is MnFeCoPBA crystals, and the core is MnCoPBA crystals.
[0012] Preferably, the time of the second coordination reaction is 4 hours, the multi-metal-based Prussian blue analogue is a MnFeCoPBA crystal, and the morphology of the multi-metal-based Prussian blue analogue is a hollow structure.
[0013] Preferably, the temperature of the second coordination reaction is 65-70°C.
[0014] Preferably, the surfactant is sodium dodecyl sulfate;
[0015] The mass ratio of the manganese acetate to the surfactant is 1:(3-4).
[0016] Preferably, the mass ratio of the manganese acetate to the potassium cobalt cyanide is 1:(1.5-2); the first coordination reaction is carried out under static conditions, and the time of the first coordination reaction is 15-20 minutes.
[0017] Preferably, the mass ratio of the manganese acetate to the potassium ferrocyanide is 1:(0.2-0.3).
[0018] Preferably, the MnCoPBA solution and potassium ferrocyanide are mixed to obtain a mixed solution; after obtaining the mixed solution and before performing the second coordination reaction, the method further comprises: allowing the mixed solution to stand at room temperature for 15 to 20 minutes.
[0019] Preferably, after the second coordination reaction is completed, a second coordination reaction liquid is obtained, and after obtaining the second coordination reaction liquid, the second coordination reaction liquid also includes: washing and drying the solid product in the second coordination reaction liquid in sequence to obtain the multi-metallic Prussian blue analog crystals; the drying is vacuum drying, and the vacuum drying temperature is 80-85°C.
[0020] The present invention provides a method for regulating the crystal morphology of a multi-metallic Prussian blue analog by using ligand competitive coordination, comprising the following steps: mixing manganese acetate, a surfactant, potassium cobalt cyanide and water for a first coordination reaction to obtain a MnCoPBA solution; mixing the MnCoPBA solution with potassium ferrocyanide for a second coordination reaction, controlling the duration of the second coordination reaction, and obtaining a series of multi-metallic Prussian blue analog crystals with different morphologies; the multi-metallic Prussian blue analog crystals include MnFeCoPBA crystals. The present invention first pre-prepares a MnCo-based Prussian blue analog (MnCoPBA), and then by reasonably adding [Fe(CN)6] 3- Anion, as the reaction time changes, [Co(CN)6] 3- and [Fe(CN)6] 3- With Mn 2+ Competitive coordination, the formation of MnFe phase and the disintegration of MnCo phase lead to the evolution of the morphology of the multi-metallic Prussian blue analogue crystal, which is specifically manifested as: MnFeCoPBA first grows epitaxially along a part of the crystal surface of MnCoPBA, and then evolves into a core-shell structure morphology, and the MnFeCoPBA thin shell continues to grow and the MnCoPBA core continues to disintegrate, and finally the MnFeCoPBA shell continues to grow and the MnCoPBA core completely disintegrates. In summary, the morphology of the multi-metallic Prussian blue analogue crystal obtained by the present invention changes from epitaxial growth to core-shell structure and then to hollow structure, and the element distribution of multi-metallic Prussian blue analogue crystals of different morphologies includes manganese, iron, cobalt, carbon and nitrogen. The present invention obtains the multi-metallic Prussian blue analogue crystals of different morphologies by controlling the reaction time; at the same time, the obtained multi-metallic Prussian blue analogue crystals have high purity and good crystallinity. The method provided by the present invention has high yield and strong repeatability, low cost, simple operation, safe reaction, short time, high purity and uniform morphology of the obtained product. The method provided by the present invention is suitable for industrial application, and the prepared composite material with complex multi-morphology can be widely used in the fields of energy catalysis and the like.
[0021] Further, in the present invention, the time of the second coordination reaction is 30 minutes, and the morphology of the multi-metallic Prussian blue analogue (named MnFeCoPBA-I) is that the MnFeCoPBA crystal is epitaxially grown on a partial area of the surface of the MnCoPBA crystal; specifically, when the morphology of the MnCoPBA crystal is a cube, the MnFeCoPBA crystal is epitaxially grown on the eight vertex areas of the cube of the MnCoPBA crystal (epitaxial growth morphology). The time of the second coordination reaction is 2 hours, and the morphology of the multi-metallic Prussian blue analogue (named MnFeCoPBA-II) is a core-shell structure, the shell is MnFeCoPBA crystal, and the core is MnCoPBA crystal (core-shell structure morphology). The time of the second coordination reaction is 4 hours, and the morphology of the multi-metallic Prussian blue analogue (named MnFeCoPBA-III) is a hollow structure (hollow morphology). The present invention adopts a ligand-induced competitive coordination method to synthesize a trimetallic MnFeCoPBA series material, controls the reaction time, and the morphologies thereof are epitaxial growth, core-shell structure, and hollow morphology, respectively. The present invention provides a new idea for regulating multimetallic Prussian blue analogs with complex morphologies. BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Figure 1 A schematic diagram of the PBA composite material prepared by the present invention;
[0023] Figure 2 This is a scanning electron microscope image of the MnCoPBA crystal prepared at room temperature with a reaction time of 15 min;
[0024] Figure 3 This is a scanning electron microscope image of the epitaxial growth crystal of MnFeCoPBA-I prepared by reacting at 70°C for 30 minutes;
[0025] Figure 4 This is a scanning electron micrograph of MnFeCoPBA-II core-shell crystals prepared by reaction at 70°C for 4 hours;
[0026] Figure 5 This is a scanning electron micrograph of MnFeCoPBA-III hollow crystals prepared by reaction at 70°C for 6 hours;
[0027] Figure 6 is the X-ray powder diffraction pattern of the prepared MnFeCoPBA crystal;
[0028] Figure 7 is the infrared spectrum of the prepared MnFeCoPBA crystal;
[0029] Figure 8 is the Raman spectrum of the prepared MnFeCoPBA crystal;
[0030] Fig. 9 is the nitrogen adsorption isotherm of the prepared MnFeCoPBA crystal;
[0031] Fig.10 is the pore size distribution curve of the prepared MnFeCoPBA crystal;
[0032] Fig.11 A reaction principle diagram of a method for regulating the crystal morphology of multi-metallic Prussian blue analogs by using ligand competitive coordination provided in an embodiment of the present invention. DETAILED DESCRIPTION
[0033] The present invention provides a method for regulating the crystal morphology of a multi-metal-based Prussian blue analog by using ligand competitive coordination, comprising the following steps:
[0034] Manganese acetate, a surfactant, potassium cobalt cyanide and water are mixed to perform a first coordination reaction to obtain a MnCoPBA solution;
[0035] The MnCoPBA solution and potassium ferrocyanide are mixed to carry out a second coordination reaction, and the duration of the second coordination reaction is controlled to obtain a series of multi-metallic Prussian blue analog crystals with different morphologies; the multi-metallic Prussian blue analog crystals include MnFeCoPBA crystals.
[0036] In the present invention, unless otherwise specified, all preparation raw materials / components are commercially available products well known to those skilled in the art.
[0037] The present invention mixes manganese acetate, a surfactant, potassium cobalt cyanide (K3[Co(CN)6]) and water (hereinafter referred to as the first mixing) to perform a first coordination reaction to obtain a MnCoPBA solution. In the present invention, the manganese acetate is preferably manganese acetate tetrahydrate (Mn(CH3COO)2·4H2O). The surfactant is preferably sodium dodecyl sulfate (SDS). The water is preferably ultrapure water. The mass ratio of the manganese acetate to the surfactant is preferably 1:(3-4), and is preferably 1:3.75. The mass ratio of the manganese acetate to the potassium cobalt cyanide is preferably 1:(1.5-2), and is preferably 1:1.65. The first mixing preferably includes: first dissolving manganese acetate and the surfactant in part of the water to obtain a manganese salt mixed solution; second dissolving potassium cobalt cyanide in the remaining water to obtain a cobalt salt solution; mixing the manganese salt solution and the cobalt salt solution. The ratio of the mass of the manganese acetate to the volume of part of the water is preferably 80 mg:3 mL. The ratio of the mass of the potassium cobalt cyanide to the volume of the remaining water is preferably 132 mg:5 mL. The first dissolution is preferably carried out under stirring and / or ultrasonic conditions, and the second dissolution is preferably carried out under stirring conditions. In the present invention, the first coordination reaction is preferably carried out in a pressure-resistant tube, the first coordination reaction is preferably carried out under static conditions, and the time of the first coordination reaction is preferably 15 to 20 minutes.
[0038] In the present invention, the MnCoPBA solution contains MnCoPBA crystals. The MnCoPBA crystals are in the shape of cubes.
[0039] After obtaining the MnCoPBA solution, the present invention mixes the MnCoPBA solution and potassium ferrocyanide (K3[Fe(CN)6]) (hereinafter referred to as the second mixing) to perform a second coordination reaction, controls the duration of the second coordination reaction, and obtains a series of multi-metallic Prussian blue analog crystals with different morphologies; the multi-metallic Prussian blue analog crystals include MnFeCoPBA crystals. In the present invention, the mass ratio of the manganese acetate and the potassium ferrocyanide is preferably 1:(0.2-0.3), and more preferably 1:0.275. During the second mixing, the potassium ferrocyanide is preferably mixed in the form of a potassium ferrocyanide aqueous solution, the water of the potassium ferrocyanide aqueous solution is preferably ultrapure water, and the ratio of the mass of potassium ferrocyanide in the potassium ferrocyanide aqueous solution to the volume of the water is preferably 22 mg:0.5 mL. In the present invention, the MnCoPBA solution and potassium ferrocyanide are mixed to obtain a mixed solution; after obtaining the mixed solution, before performing the second coordination reaction, the present invention preferably further comprises: allowing the mixed solution to stand at room temperature, and the standing time is preferably 15 to 20 minutes, and more preferably 15 minutes. The second coordination reaction is preferably carried out in a pressure-resistant tube. When carrying out the second coordination reaction, the present invention preferably places the pressure-resistant tube containing the mixed solution on a heating table for constant temperature reaction, and the heating table is preferably an aluminum block heating table. The temperature of the second coordination reaction is preferably 65 to 70°C, and specifically preferably 70°C. The insulation time of the second coordination reaction is preferably ≥30 minutes, more preferably 30 minutes to 4 hours, and specifically preferably 30 minutes, 2 hours or 4 hours.
[0040] In the present invention, the time of the second coordination reaction is 30 minutes, the multi-metallic Prussian blue analogue includes MnCoPBA crystals and MnFeCoPBA crystals, and the morphology of the multi-metallic Prussian blue analogue is that the MnFeCoPBA crystals are epitaxially grown on a partial area of the surface of the MnCoPBA crystals.
[0041] In the present invention, the morphology of the MnCoPBA crystal is a cube, the time of the second coordination reaction is preferably 30 minutes, the multi-metallic Prussian blue analogue includes MnCoPBA crystal and MnFeCoPBA crystal, the morphology of the MnCoPBA crystal is a cube, and the morphology of the multi-metallic Prussian blue analogue is that the MnFeCoPBA crystal is epitaxially grown in the eight vertices of the cube of the MnCoPBA crystal.
[0042] In the present invention, the time of the second coordination reaction is preferably 2 hours, the multi-metal-based Prussian blue analogue includes MnCoPBA crystals and MnFeCoPBA crystals, and the morphology of the multi-metal-based Prussian blue analogue is a core-shell structure, the shell layer is MnFeCoPBA crystals, and the core is MnCoPBA crystals.
[0043] In the present invention, the morphology of the MnCoPBA crystal is a cube, the time of the second coordination reaction is preferably 2h, the multi-metallic Prussian blue analogue includes MnCoPBA crystal and MnFeCoPBA crystal, the morphology of the multi-metallic Prussian blue analogue is a core-shell structure, the shell is MnFeCoPBA crystal, and the core is MnCoPBA crystal. The MnFeCoPBA crystal continues to grow along the edges of the cube of the MnCoPBA crystal by epitaxial growth in the area of the eight vertices of the cube of the MnCoPBA crystal (at 30min), extending to the face center of the cube, and the shell morphology of the obtained MnFeCoPBA crystal is a cubic skeleton shell (the central area of the six surfaces does not completely cover the core), and the core is MnCoPBA crystal.
[0044] In the present invention, the time of the second coordination reaction is preferably 4 hours, the multi-metal-based Prussian blue analogue is a MnFeCoPBA crystal, and the morphology of the multi-metal-based Prussian blue analogue is a hollow structure.
[0045] In the present invention, the morphology of the MnCoPBA crystal is a cube, the time of the second coordination reaction is preferably 4 hours, the multi-metallic Prussian blue analog is a MnFeCoPBA crystal, and the morphology of the multi-metallic Prussian blue analog is a hollow structure. During the growth of the MnFeCoPBA crystal, the MnCoPBA crystal core gradually completely disintegrates. When the second coordination reaction is 4 hours, the MnCoPBA crystal core completely disintegrates to obtain a MnFeCoPBA crystal with a hollow structure. The MnFeCoPBA crystal with a hollow structure is a cubic skeleton hollow structure.
[0046] In the present invention, the morphology of the MnCoPBA crystal is a cube, the growth of MnFeCoPBA starts along the eight corners of the MnCoPBA cube crystal and then evolves into a core-shell structure, and the MnFeCoPBA thin shell continues to grow and the MnCoPBA core begins to disintegrate, and finally the MnFeCoPBA shell continues to grow and the MnCoPBA core completely disintegrates.
[0047] In the present invention, after the second coordination reaction is completed, a second coordination reaction liquid is obtained. After obtaining the second coordination reaction liquid, the present invention preferably further comprises: washing and drying the solid product in the second coordination reaction liquid in sequence to obtain the multi-metallic Prussian blue analog crystal. The washing is preferably performed in sequence by water washing and ethanol washing (EtOH). The water used for the water washing is preferably ultrapure water. The water washing and ethanol washing are independently preferably centrifugal washing, and the number of the water washing and ethanol washing is preferably 3 times, respectively. The drying is preferably vacuum drying, and the temperature of the vacuum drying is preferably 80 to 85°C.
[0048] In summary, the present invention provides a method for regulating the morphology of multi-metallic Prussian blue analogs by ligand exchange. The method provided by the present invention uses a solid cubic or solid spherical MnCo Prussian blue analog (MnCoPBA) prepared by a controllable solvothermal method as a precursor, and by reasonably adding [Fe(CN)6] 3- Anions, as the reaction time increases, MnFeCoPBA will undergo morphological evolution. A series of MnFeCoPBA nanocrystals with different morphologies are obtained, from epitaxial growth to core-shell structure to hollow structure. The method provided by the present invention prepares a MnFeCoPBA composite material with an ideal morphology by ligand exchange and regulating reaction conditions. The method provided by the present invention is low in cost, simple to operate, and the prepared product has high purity, high yield, and strong repeatability, and can be applied to fields such as catalytic energy.
[0049] In order to further illustrate the present invention, the technical solutions provided by the present invention are described in detail below in conjunction with embodiments, but they should not be construed as limiting the protection scope of the present invention.
[0050] Example 1
[0051] (1) In a 35.0 mL pressure tube, add a mixture of 80 mg of Mn(CH3COO)2·4H2O and 300 mg of SDS to 3 mL of ultrapure water and stir to mix well.
[0052] (2) Furthermore, 132 mg of K3[Co(CN)6] (potassium cobalt cyanide) was added to 5 mL of ultrapure water and dissolved to obtain solution A.
[0053] (3) Inject solution A into a pressure-resistant tube, shake well, and let stand for 15 minutes to obtain a MnCoPBA solution.
[0054] (4) Then dissolve 22 mg of K3[Fe(CN)6] in 0.5 mL of ultrapure water to obtain solution B.
[0055] (5) Solution B was added to the uncentrifuged MnCoPBA solution and allowed to stand at room temperature for 15 min.
[0056] (6) The pressure tube was transferred to an aluminum block heating table for constant temperature reaction and placed at 70°C for 30 min, 2 h and 4 h, respectively. After natural cooling, the product was collected by washing with H2O and EtOH and centrifuging three times, and then dried in a vacuum oven at 85°C to obtain products with epitaxial growth, core-shell structure and hollow morphology, respectively, named MnFeCoPBA-I, MnFeCoPBA-II and MnFeCoPBA-III, respectively.
[0057] Figure 1 This is a schematic diagram of the PBA composite material prepared in Example 1 of the present invention.
[0058] Figure 2 The SEM images show that the micrometer-sized MnCoPBA precursor crystals present a cubic morphology; Figure 3 The middle SEM image shows the epitaxial growth of MnFeCoPBA-I along the corner; Figure 4 The core-shell structure of MnFeCoPBA-II is shown in the SEM image; Figure 5 The scanning electron microscope image shows the hollow structure of MnFeCoPBA-III.
[0059] Figure 6 As shown in the X-ray powder diffraction pattern, all the MnFeCoPBA series materials can correspond to the pure MnCoPBA precursor with good crystallinity, indicating that their crystallinity is relatively excellent.
[0060] Figure 7 The mid-infrared spectrum shows two obvious peaks, which are attributed to Co-C≡N-Mn (2162cm -1 ) and Fe-C≡N-Mn(2066cm -1 ), while the four PBA materials with different morphologies all have 2161cm -1 The characteristic peak at 3+ -C≡N-Mn 2+ The structure of MnFeCoPBA-I to MnFeCoPBA-III can be observed. 3+ -C≡N-Mn 2+ The enhancement of the characteristic peaks of the structure with reaction time indicates the competitive coordination process between the two phases during the reaction.
[0061] Figure 8 The Raman spectrum shows 2078 cm -1 and 2118cm -1 The characteristic peaks of 2172cm come from the Fe-C≡N-Mn bonds in MnFeCoPBA and MnFePBA, while -1 and 2192cm -1 The characteristic peaks come from Co-C≡N-Mn in MnCoPBA. At the same time, the peaks related to Co-C≡N-Mn gradually weaken, which is consistent with the dissolution of the MnCoPBA core in MnFeCoPBA-Ⅲ.
[0062] Fig. 9 and Fig.10The nitrogen adsorption isotherms and pore size distribution curves show that the nitrogen adsorption curves of all samples present type I isotherms and the pore size is about 0.5 nm.
[0063] in, Figure 6 to Figure 10 The MnFePBA in the mixture can be prepared by using conventional existing technology.
[0064] It can be seen from the above examples that the method provided by the present invention is not only low-cost and easy to operate, but also can prepare complex and multi-morphological composite materials that can be widely used in energy catalysis and other fields. The present invention synthesizes trimetallic MnFeCoPBA series materials by a ligand-induced competitive coordination method. First, a MnCo-based Prussian blue analogue (MnCoPBA) is prefabricated, and by reasonably adding [Fe(CN)6] 3 - anion, it was observed that the morphology of MnFeCoPBA would evolve with the reaction time, and the morphology of the obtained composite material changed from epitaxial growth to core-shell structure and then to hollow structure. This method has high yield and strong repeatability. This strategy provides a way to prepare composite materials and proposes effective regulation of morphology.
[0065] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.
Claims
1. A method for regulating the crystal morphology of a multi-metallic Prussian blue analog by ligand competitive coordination, characterized in that: The following steps are involved: Manganese acetate, a surfactant, potassium cobalt cyanide and water are mixed to perform a first coordination reaction to obtain a MnCoPBA solution; The MnCoPBA solution and potassium ferrocyanide are mixed to carry out a second coordination reaction, and the duration of the second coordination reaction is controlled to obtain multi-metallic Prussian blue analog crystals with different morphologies; the multi-metallic Prussian blue analog crystals include MnFeCoPBA crystals.
2. The method for regulating the crystal morphology of multi-metallic Prussian blue analogs by ligand competitive coordination according to claim 1, characterized in that: The time of the second coordination reaction is 30 minutes. The multi-metal-based Prussian blue analogue includes MnCoPBA crystals and MnFeCoPBA crystals. The morphology of the multi-metal-based Prussian blue analogue is that the MnFeCoPBA crystals are epitaxially grown on a partial area of the surface of the MnCoPBA crystals.
3. The method for regulating the crystal morphology of a multi-metallic Prussian blue analog by ligand competitive coordination according to claim 1, characterized in that: The time of the second coordination reaction is 2 hours. The multi-metal-based Prussian blue analogue includes MnCoPBA crystals and MnFeCoPBA crystals. The morphology of the multi-metal-based Prussian blue analogue is a core-shell structure, the shell layer is MnFeCoPBA crystals, and the core is MnCoPBA crystals.
4. The method for regulating the crystal morphology of a multi-metallic Prussian blue analog by ligand competitive coordination according to claim 1, characterized in that: The time of the second coordination reaction is 4 hours, the multi-metal-based Prussian blue analogue is a MnFeCoPBA crystal, and the morphology of the multi-metal-based Prussian blue analogue is a hollow structure.
5. The method for regulating the crystal morphology of a multi-metallic Prussian blue analog by using ligand competitive coordination according to any one of claims 1 to 4, characterized in that: The temperature of the second coordination reaction is 65-70°C.
6. The method for regulating the crystal morphology of a multi-metallic Prussian blue analogue by using ligand competitive coordination according to any one of claims 1 to 4, characterized in that: The surfactant is sodium lauryl sulfate; The mass ratio of the manganese acetate to the surfactant is 1:(3-4).
7. The method for regulating the crystal morphology of a multi-metallic Prussian blue analog by using ligand competitive coordination according to any one of claims 1 to 4, characterized in that: The mass ratio of the manganese acetate to the potassium cobalt cyanide is 1:(1.5-2); the first coordination reaction is carried out under static conditions, and the time of the first coordination reaction is 15-20 minutes.
8. The method for regulating the crystal morphology of a multi-metallic Prussian blue analogue by using ligand competitive coordination according to any one of claims 1 to 4, characterized in that: The mass ratio of the manganese acetate to the potassium ferrocyanide is 1:(0.2-0.3).
9. The method for regulating the crystal morphology of a multi-metallic Prussian blue analog by using ligand competitive coordination according to any one of claims 1 to 4, characterized in that: The MnCoPBA solution and potassium ferrocyanide are mixed to obtain a mixed solution; After obtaining the mixed solution and before carrying out the second coordination reaction, the method further comprises: allowing the mixed solution to stand at room temperature for 15 to 20 minutes.
10. The method for regulating the crystal morphology of a multi-metallic Prussian blue analogue by using ligand competitive coordination according to any one of claims 1 to 4, characterized in that: After the second coordination reaction is completed, a second coordination reaction liquid is obtained. After obtaining the second coordination reaction liquid, the method also includes: washing and drying the solid product in the second coordination reaction liquid in sequence to obtain the multi-metallic Prussian blue analog crystals; the drying is vacuum drying, and the vacuum drying temperature is 80-85°C.