CN112048072A - Preparation method of Hoffman type coordination polymer nano material - Google Patents

Preparation method of Hoffman type coordination polymer nano material Download PDF

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CN112048072A
CN112048072A CN202010794462.0A CN202010794462A CN112048072A CN 112048072 A CN112048072 A CN 112048072A CN 202010794462 A CN202010794462 A CN 202010794462A CN 112048072 A CN112048072 A CN 112048072A
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hoffman
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佴建威
徐祥蓁
陶新永
赵新月
卢功勋
居治金
王垚
刘铁峰
刘育京
周詹琦
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Zhejiang University of Technology ZJUT
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Abstract

A preparation method of a Hoffman type coordination polymer nano material comprises the following steps: dissolving a metal M salt, trisodium citrate and a surfactant in a solvent to obtain a mixed solution; will K2[M′(CN)4]Dissolving in deionized water to obtain K2[M′(CN)4]A solution; will K2[M′(CN)4]Adding the solution into the mixed solution, stirring, aging at room temperature for 4-48 h, and cleaning, centrifuging and drying the formed precipitate to obtain the compound; the micro-nano material prepared by the method has the characteristics of multiple dimensions, multiple growth modes and uniform size, the method has certain universality, a new reference can be provided for preparing other similar cyano-bridged metal framework coordination polymers, and the synthesized Hofmann coordination polymer nano material has potential in the field of photoelectrocatalysisHas wide application foreground.

Description

Preparation method of Hoffman type coordination polymer nano material
Technical Field
The invention belongs to the technical field of preparation of inorganic compound functional materials, and particularly relates to a Hoffman type coordination polymer (recorded as M)IILxM′II(CN)4·yH2O) a preparation method of the micro-nano material.
Background
In recent years, two-dimensional nanomaterials are receiving more and more attention due to their unique two-dimensional related physical and chemical properties, and typical two-dimensional nanomaterials, such as graphene, transition metal sulfides and layered hydroxide nanosheets, are widely researched and applied in the fields of electronic products, energy storage, sensors, catalysis and the like, so that functional nanomaterials are always hot spots of nanotechnology research. Since the preparation of nanomaterials is the basis of nanotechnology research, the preparation methodology is of great interest. In recent years, research directions of researchers have been changed from a method for preparing nano materials with only one structure (morphology or composition) to a method for designing a universal preparation route, so as to obtain nano materials with different structures.
Metal-framed coordination polymers bridged by cyano groups, of the general formula MIIL2M′II(CN)4Wherein M is a 2-valent transition metal, forms a coordinated octahedron with 4N atoms of cyano groups and 2 further ligands L, L being a bidentate or two monodentate molecule, typically comprising ligands containing unsaturated NMolecules such as pyridine, ammonia, and pyridine derivatives; ligand molecules containing unsaturated O, e.g. H2O, dioxane, DMF, urea, etc.; unsaturated S-containing ligand molecules, such as 1, 3-thiazole-2-thionyl chloride, dimethylthiocarboxamide, M 'is another divalent transition metal (M' ═ Ni, Pd, Pt), form square planar coordination with cyanide molecules. Coordination bonds to cyano groups and transition metals are similar to covalent bonds and have very high strength, enabling molecules to coordinate to other metals due to the high lewis basicity of tetracyanometalates. Therefore, the two-dimensional coordination polymer bridged by the cyano group presents different crystal structures and micro morphologies under the action of the ligand L, and the structural transformation is expected to occur during the coordination action of the L without destroying the coordination network, which is of great significance for better understanding of the structural transformation of the flexible Coordination Polymers (CPs).
The hoffman-type coordination polymer nano material is a new problem in recent years, reports are few, and the number of types of synthesis of the coordination polymer is limited due to the advantages that more active sites can be exposed when the hoffman-type coordination polymer nano material reacts with reactants in a photoelectrocatalysis reaction, mass transfer in a system is rapid, and the like.
Disclosure of Invention
The invention provides a new method for synthesizing [ M ]′II(CN)4]2-The preparation method of the Hofmann coordination polymer nano material for basically constructing the basic elements has the advantages of simple operation, controllable size and morphology, certain universality and capability of providing a new reference for preparing other similar cyano-bridged metal framework coordination polymers.
By introducing a metal inorganic salt M2+And K2[M′(CN)4]As a precursor, trisodium citrate as a metal ion complexing agent and a proper surfactant, a series of M with different components, sizes and shapes are prepared in different solvent systemsIILxM′II(CN)4·yH2O micro-nano material. Wherein the different components comprise: m (H)2O)x[M′(CN)4]·yH2O、M(DMF)x[M′(CN)4]·yH2O、M(MeCN)x[M′(CN)4]·yH2O; m ═ Pt, Co, Ni, or Mn; m ═ Ni or Pt. The different morphologies include: hexagonal, octagonal, rectangular and square micron sheets and micron sheet assemblies thereof.
The technical scheme of the invention is as follows:
a preparation method of a Hoffman type coordination polymer nano material comprises the following steps:
dissolving a metal M salt, trisodium citrate and a surfactant in a solvent to obtain a mixed solution; will K2[M′(CN)4]Dissolving in deionized water to obtain K2[M′(CN)4]A solution; will K2[M′(CN)4]Adding the solution into the mixed solution, stirring (1min), aging at room temperature (20-30 ℃) for 4-48 h, cleaning (with absolute ethyl alcohol and deionized water) a formed precipitate, centrifuging, and drying (at 70 ℃ for 8-12 h) to obtain the Hoffman type coordination polymer nano material;
the metal M salt, trisodium citrate and K2[M′(CN)4]The ratio of the amounts of substances (1): 0.1-1.5: 1;
the mass usage of the surfactant is 1-10 g/mmol based on the mass of the metal M salt;
m in the metal M salt is Pt, Co, Ni or Mn; specifically, the metal M salt is, for example: ni (Ac)2·4H2O、K2PtCl4、Co(Ac)2·4H2O、Mn(Ac)2·4H2O；
The surfactant is selected from one or more of polyvinylpyrrolidone (PVP), Sodium Dodecyl Sulfate (SDS) and dodecyl trimethyl ammonium bromide (CTAB);
said K2[M′(CN)4]Represents K2Ni(CN)4Or K2Pt(CN)4；
The solvent is deionized water, or the volume ratio of the deionized water to the organic solvent is 1-2: 1, a mixed solvent; the organic solvent is selected from dimethyl sulfoxide, N-dimethylacetamide, dimethyl imidazolidinone, hexamethylphosphoric triamide, N-methylformamide, N-dimethylformamide, acetonitrile or L-cysteine;
the volume usage of the solvent is 10-150 mL/mmol based on the amount of the metal M salt;
said K2[M′(CN)4]The concentration of the solution is 0.02-0.075 mmol/mL.
The general formula of the Hoffman type coordination polymer nano material prepared by the invention is MIILxM′II(CN)4·yH2O, wherein: m ═ Pt, Co, Ni, or Mn, M ═ Ni, or Pt, L ═ H2O, MeCN or DMF, x is 1-2, y is 1-6; the method specifically comprises the following steps: m (H)2O)x[M′(CN)4]·yH2O、M(DMF)x[M′(CN)4]·yH2O、M(MeCN)x[M′(CN)4]·yH2O。
Further, the Hoffman type coordination polymer nano material:
when M ═ Ni, PVP as surfactant, H as solvent2O is Ni (H)2O)x[Ni(CN)4]·yH2O, the product is uniform, sharp and clear-cut, regular hexagonal micron sheet with size of about 2 μm. The crystal belongs to an orthorhombic system, wherein the Ni atom connected with N is coordinated by 4 cyano-N atoms and water molecules to form an octahedral coordination sphere, and the Ni atom connected with C is coordinated by only 4C atoms to form a square plane coordination environment. Two Ni atoms are connected on the same plane through cyano groups to form a two-dimensional cyano-bridged metal framework layered structure.
When M ═ Co, M ═ Ni, PVP as surfactant, H as solvent2When O is present, the molecular formula is Co (H)2O)x[Ni(CN)4]·yH2And O, the product is a regular hexagonal micron sheet with sharp and clear outline. The crystal belongs to an orthorhombic system, wherein a Co atom is coordinated by 4 cyano-N atoms and water molecules to form an octahedral coordination sphere, a Ni atom is in a four-coordinated planar coordination environment, and the Co atom and the Ni atom are connected through a cyano group to form a two-dimensional cyano-bridged metal framework layered structure.
When M ═ Ni, M' ═ Ni,the surfactant is PVP, and the molecular formula is Ni (H) when the solvent contains dimethyl sulfoxide2O)x[Ni(CN)4]·yH2And O, under the influence of polar molecule dimethyl sulfoxide, the product has uniform appearance, sharp and clear profile and regular square micron sheets with the size of about 5 microns. The crystal belongs to an orthorhombic system, wherein the Ni atom connected with N is coordinated by 4 cyano-N atoms and water molecules to form an octahedral coordination sphere, and the Ni atom connected with C is coordinated by only 4C atoms to form a square plane coordination environment. Two Ni atoms are connected on the same plane through cyano groups to form a two-dimensional cyano-bridged metal framework layered structure.
When M ═ Ni, M ═ Pt, PVP as a surfactant and dimethyl sulfoxide as a solvent are used, the molecular formula is Ni (H)2O)x[Pt(CN)4]·yH2And O, under the influence of polar molecule dimethyl sulfoxide, the product has uniform appearance, sharp and clear profile and regular square micron sheets with the size of about 5 microns. The crystal belongs to an orthorhombic system, wherein Ni atoms connected with N are coordinated by 4 cyano-N atoms and water molecules to form octahedral coordination spheres, and Pt atoms connected with C are coordinated by only 4C atoms to form a square plane coordination environment. Ni and Pt atoms are connected on the same plane through cyano groups to form a two-dimensional cyano-bridged metal framework layered structure.
When M ═ Pt, M ═ Ni, PVP as a surfactant and dimethyl sulfoxide as a solvent are used, the molecular formula is Pt (H)2O)x[Ni(CN)4]·yH2And O, under the influence of polar molecule dimethyl sulfoxide, the product has uniform appearance, sharp and clear profile and regular square micron sheets with the size of about 2 microns. The crystal belongs to an orthorhombic system, wherein Ni atoms connected with N are coordinated by 4 cyano-N atoms and water molecules to form octahedral coordination spheres, and Pt atoms connected with C are coordinated by only 4C atoms to form a square plane coordination environment. Ni and Pt atoms are connected on the same plane through cyano groups to form a two-dimensional cyano-bridged metal framework layered structure.
When M ═ Ni, the surfactant is PVP, and the solvent contains N, N-bisWhen methyl acetamide, the molecular formula is Ni (H)2O)x[Ni(CN)4]·yH2O, under the influence of polar molecule N, N-dimethylacetamide, the product has uniform appearance, sharp and clear profile and regular hexagonal micron sheet size of about 7 microns. The crystal belongs to an orthorhombic system, wherein the Ni atom connected with N is coordinated by 4 cyano-N atoms and water molecules to form an octahedral coordination sphere, and the Ni atom connected with C is coordinated by only 4C atoms to form a square plane coordination environment. Two Ni atoms are connected on the same plane through cyano groups to form a two-dimensional cyano-bridged metal framework layered structure.
When M ═ Ni, PVP as a surfactant and dimethyl imidazolidinone as a solvent are contained, Ni (H) as a molecular formula2O)x[Ni(CN)4]·yH2O, under the induction of solvent molecule dimethyl imidazolidinone, the morphology of the product presents uniform and sharply defined truncated octagonal micron sheets, and the size of the octagon micron sheets is about 3 mu m. The crystal belongs to an orthorhombic system, wherein the Ni atom connected with N is coordinated by 4 cyano-N atoms and water molecules to form an octahedral coordination sphere, and the Ni atom connected with C is coordinated by only 4C atoms to form a square plane coordination environment. Two Ni atoms are connected on the same plane through cyano groups to form a two-dimensional cyano-bridged metal framework layered structure.
When M ═ Ni, PVP as a surfactant and hexamethylphosphoric triamide as a solvent are contained, Ni (H) is represented by the formula2O)x[Ni(CN)4]·yH2O, under the induction of solvent molecule hexamethylphosphoric triamide, the product has uniform appearance, sharp and clear outline and regular rectangular micron sheet with the size of about 2 x 3 μm. The crystal belongs to an orthorhombic system, wherein the Ni atom connected with N is coordinated by 4 cyano-N atoms and water molecules to form an octahedral coordination sphere, and the Ni atom connected with C is coordinated by only 4C atoms to form a square plane coordination environment. Two Ni atoms are connected on the same plane through cyano groups to form a two-dimensional cyano-bridged metal framework layered structure.
When M ═ Ni, the surfactant is PVP, and the solvent contains N-methylWhen it is amide, the molecular formula is Ni (H)2O)x[Ni(CN)4]·yH2And O, under the induction of solvent molecule N-methylformamide, the morphology of the product presents nano flakes with larger specific surface area. The crystal belongs to an orthorhombic system, wherein the Ni atom connected with N is coordinated by 4 cyano-N atoms and water molecules to form an octahedral coordination sphere, and the Ni atom connected with C is coordinated by only 4C atoms to form a square plane coordination environment. Two Ni atoms are connected on the same plane through cyano groups to form a two-dimensional cyano-bridged metal framework layered structure.
When M ═ Ni, the surfactant is PVP and the solvent contains N, N-dimethyl formamide, the molecular formula is Ni (DMF)x[Ni(CN)4]·yH2O, under the induction of solvent molecule N, N-dimethyl formamide, the product has homogeneous and sharp and clear contour and regular three-dimensional micron sheet assembly with the oxygen in DMF molecule providing electron and Ni [ Ni (CN)4]Ni bonded to N in the molecule forms a coordinate bond and is present in Ni [ Ni (CN)4]Each layer of the molecule is directionally assembled along one direction through the interaction of methyl on DMF molecules, and a three-dimensional cyano-bridged metal framework structure is assembled, wherein the transverse dimension is 2 mu m, and the longitudinal dimension is 1.5 mu m. The crystal belongs to a monoclinic system, wherein the Ni atom connected with N is coordinated by 4 cyano-N atoms and DMF molecules to form an octahedral coordination sphere, and the Ni atom connected with C is coordinated by only 4C atoms to form a square plane coordination environment. Two Ni atoms are connected on the same plane through cyano-groups, and the planes are directionally connected through DMF molecules to form a three-dimensional cyano-bridged metal framework layered structure.
When M ═ Ni, the surfactant PVP + SDS and the solvent contain N, N-dimethylformamide, the molecular formula is Ni (DMF)x[Ni(CN)4]·yH2And O, under the induction of solvent molecules of N, N-dimethylformamide and SDS, the morphology of the product is changed from a square three-dimensional micron sheet assembly into a truncated octagonal three-dimensional micron sheet assembly.
When M ═ Ni, the surfactant is SDS, and the solvent contains N, N-bisWhen methyl formamide is used, the molecular formula is Ni (DMF)x[Ni(CN)4]·yH2And O, under the induction of solvent molecules of N, N-dimethylformamide and SDS, the appearance of the product is transformed into a square three-dimensional micron sheet assembly with a very smooth surface.
When the surfactant is PVP and the solvent contains N, N-dimethylformamide, the molecular formula is Co (DMF)x[Ni(CN)4]·yH2O, under the induction of solvent molecule N, N-dimethyl formamide, the product has homogeneous and sharp and clear contour and regular three-dimensional micron sheet hollow assembly, in which the oxygen in DMF provides electron and Co [ Ni (CN)4]Forming a coordinate bond with a Co atom in the molecule, and in Co [ Ni (CN)4]Each layer of the molecule is directionally assembled along one direction through the interaction of methyl on DMF molecules, and a three-dimensional cyano-bridged metal framework structure is assembled, wherein the transverse dimension is 2 mu m, and the longitudinal dimension is 1.5 mu m. The crystal belongs to a monoclinic system, wherein a Co atom is coordinated by 4 cyano-N atoms and DMF molecules to form an octahedral coordination sphere, and a Ni atom connected with C is coordinated by only 4C atoms to form a square plane coordination environment. Co and Ni atoms are connected on the same plane through cyano-groups, and the planes are directionally connected through DMF molecules to form a three-dimensional cyano-bridged metal framework layered structure.
When M ═ Mn, M ═ Ni, PVP as surfactant and N, N-dimethylformamide as solvent, the molecular formula is Mn (DMF)x[Ni(CN)4]·yH2O, under the induction of solvent molecule N, N-dimethyl formamide, the product has homogeneous, sharp and clear contour and regular three-dimensional micron sheet assembly, in which the oxygen in DMF provides electron and Mn [ Ni (CN)4]Forming a coordinate bond with the Mn atom in the molecule, and in Mn [ Ni (CN)4]And (3) directionally assembling each plane unit along one direction through the interaction of methyl on DMF molecules among each layer of the molecules to assemble the three-dimensional cyano-bridged metal framework type structure. The crystal belongs to monoclinic system, wherein Mn atom is coordinated by 4 cyano-N atoms and DMF molecule to form octahedral coordination sphere, and Ni atom connected with C is only coordinated by 4C atomsThe atoms coordinate to form a square plane coordination environment. Mn atoms and Ni atoms are connected on the same plane through cyano groups, and the planes are directionally connected through DMF molecules to form a three-dimensional cyano-bridged metal framework layered structure.
When M ═ Ni, PVP and acetonitrile are used as surfactant, the molecular formula is Ni (MeCN)x[Ni(CN)4]·yH2O, under the induction of solvent molecule acetonitrile, the appearance of the product presents a uniform, sharp and clear-cut and regular three-dimensional vertical orthogonal nanosheet assembly, wherein the cyano group of the MeCN molecule converts the tetracyano group in a two-dimensional configuration into hexacyano group in a three-dimensional configuration, so that the crystal is directionally assembled along three mutually perpendicular directions with the size of 1.5 mu m when growing. The crystal belongs to a face-centered cubic system, and MeCN molecules are used as a structure directing agent to participate in the crystal structure, so that the nanosheets are orderly assembled according to a three-dimensional orthogonal mode to form a three-dimensional orthogonal assembled cyano-bridged metal framework structure.
When the surfactant is PVP and the solvent contains acetonitrile, the molecular formula is Co (MeCN)x[Ni(CN)4]·yH2O, under the induction of solvent molecule acetonitrile, the appearance of the product presents a uniform, sharp and clear-cut and regular three-dimensional vertical orthogonal nanosheet assembly, wherein the cyano group of the MeCN molecule converts the tetracyano group in a two-dimensional configuration into hexacyano group in a three-dimensional configuration, so that the crystal is directionally assembled along three mutually perpendicular directions with the size of 1.5 mu m when growing. The crystal belongs to a face-centered cubic system, and MeCN molecules are used as a structure directing agent to participate in the crystal structure, so that the nanosheets are orderly assembled according to a three-dimensional orthogonal mode to form a three-dimensional orthogonal assembled cyano-bridged metal framework structure.
Compared with the prior art, the invention has the following beneficial effects:
the invention has the advantages of simple preparation method, high repeatability, small synthesized particle size at low temperature, narrow distribution range and the like.
The Hoffman type coordination polymer nano material has certain thermal stability, wherein Ni (H)2O)x[Ni(CN)4]·yH2O and Ni (DMF)x[Ni(CN)4]·yH2The temperature for removing water molecules and DMF molecules from O is 180 ℃ and 300 ℃, and the skeleton decomposition temperature is about 400 ℃.
The described Ni (DMF)x[Ni(CN)4]·yH2O and Ni (MeCN)x[Ni(CN)4]·yH2The O-type Hoffman coordination polymer has high coordination bond strength between the assembly molecules and the micron sheet elements and good stability, and is not removed when the temperature is respectively raised to the boiling points of DMF molecules and MeCN molecules.
The micro-nano material prepared by the method has the characteristics of multiple dimensions, multiple growth modes and uniform size. The method has certain universality, can provide a new reference for preparing other similar cyano-bridged metal framework coordination polymers, and the synthesized Hofmann type coordination polymer nano material has potential application prospect in the field of photoelectrocatalysis.
Drawings
FIGS. 1A to 1C are Hofmann coordination polymers Ni (H) prepared in examples 1 to 6 respectively in a solvent molecular system of deionized water, dimethyl sulfoxide, N-dimethylacetamide, dimethyl imidazolidinone, hexamethylphosphoric triamide, N-methylformamide2O)x[Ni(CN)4]·yH2SEM, XRD, and FTIR patterns of O; a) deionized water; b) dimethyl sulfoxide; c) dimethyl imidazolidinone; d) n, N-dimethylacetamide; e) hexamethylphosphoric triamide; f) n-methylformamide.
FIGS. 2A to 2C are Hoffman-type coordination polymers Ni (H) prepared in examples 7 to 8 under a dimethyl sulfoxide system2O)x[Pt(CN)4]·yH2O and Pt (H)2O)x[Ni(CN)4]·yH2SEM, XRD, and FTIR patterns of O; a) m ═ Ni, M ═ Pt; b) m ═ Pt, M ═ Ni.
FIGS. 3A-3C are three-dimensional cyano-bridged metal framework layered structures M (DMF) prepared in N, N-dimethylformamide solvent molecule of examples 9-11x[Ni(CN)4]·yH2SEM, XRD and FTIR patterns of O, M ═ Ni, Co, Mn; a) m ═ Ni; b) m ═ Co；c)M＝Mn。
FIGS. 4A-4C are three-dimensional cyano-bridged metal framework layered structures M (MeCN) prepared in acetonitrile solvent molecules of examples 14-15x[Ni(CN)4]·yH2SEM, XRD and FTIR patterns of O, M ═ Ni, Co; a) m ═ Ni; b) and M is Co.
FIG. 5 is a Hoffman-type coordination polymer Ni (H) prepared in a deionized water system of a comparative example2O)x[Ni(CN)4]·yH2SEM and XRD patterns of O; a) XRD; b) SEM.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples, but the scope of the present invention is not limited thereto.
Example 1
1.5mmol of Ni (Ac)2·4H2O, 1.9mmol trisodium citrate and 4.0g PVP (molecular weight 40000) were dissolved in 20mL H2Forming a solution A in the O, and magnetically stirring at a certain speed; 1.5mmol K2Ni(CN)4Dissolved in 20mL of H2O, forming a solution B. Then, the solution B was slowly poured into the solution A over 5s, and after continuing to stir for 1 minute, the mixed solution was aged at room temperature for 24 hours. The obtained precipitate was washed with absolute ethanol and deionized water 3 times, centrifuged, dried at 70 ℃ overnight, and the sample was collected.
Example 2
1.5mmol of Ni (Ac)2·4H2O, 1.9mmol trisodium citrate and 4.0g PVP (molecular weight 40000) were dissolved in 25mL H2Forming a solution A in a mixed solution of O and 20mL of DMSO, and magnetically stirring at a certain speed; 1.5mmol K2Ni(CN)4Dissolved in 20mL of H2O, forming a solution B. Then solution B was slowly poured into solution A over 5s, and after stirring was continued for 1 minute, the mixed solution was aged at room temperature for 12 hours. The obtained precipitate was washed with absolute ethanol and deionized water 3 times, centrifuged, dried at 70 ℃ overnight, and the sample was collected.
Example 3
1.5mmol of Ni (Ac)2·4H2O, 1.5mmol trisodium citrate and 2.0g PVP (molecular weight 40000) were dissolved in 30mL H2Forming a solution A in O and 15mL of N, N-dimethylacetamide, and magnetically stirring at a certain speed; 1.5mmol K2Ni(CN)4Dissolved in 20mL of H2O, forming a solution B. Then, the solution B was slowly poured into the solution A over 5s, and after continuing to stir for 1 minute, the mixed solution was aged at room temperature for 24 hours. The obtained precipitate was washed with absolute ethanol and deionized water 3 times, centrifuged, dried at 70 ℃ overnight, and the sample was collected.
Example 4
1.5mmol of Ni (Ac)2·4H2O, 1.5mmol trisodium citrate and 2.0g PVP (molecular weight 40000) were dissolved in 30mL H2Forming a solution A in O and 15mL of dimethyl imidazolidinone, and magnetically stirring at a certain speed; 1.5mmol K2Ni(CN)4Dissolved in 20mL of H2O, forming a solution B. Then, the solution B was slowly poured into the solution A over 5s, and after stirring was continued for 1 minute, the mixed solution was aged at room temperature for 12 hours. The obtained precipitate was washed with absolute ethanol and deionized water 3 times, centrifuged, dried at 70 ℃ overnight, and the sample was collected.
Example 5
1.5mmol of Ni (Ac)2·4H2O, 1.0mmol of trisodium citrate and 2.0g of PVP (molecular weight 40000) in 30mL of H2Forming a solution A in O and 15mL of hexamethylphosphoric triamide, and magnetically stirring at a certain speed; 1.5mmol K2Ni(CN)4Dissolved in 20mL of H2O, forming a solution B. Then, the solution B was slowly poured into the solution A over 5s, and after stirring was continued for 1 minute, the mixed solution was aged at room temperature for 12 hours. The obtained precipitate was washed with absolute ethanol and deionized water 3 times, centrifuged, dried at 70 ℃ overnight, and the sample was collected.
Example 6
1.5mmol of Ni (Ac)2·4H2O, 1.9mmol trisodium citrate and 2.0g PVP (molecular weight 40000) were dissolved in 15mL H2Forming a solution A in O and 15mL of N-methylformamide, and magnetically stirring at a certain speed; 1.5mmol K2Ni(CN)4Dissolved in 20mL of H2O, forming a solution B. Then slowly pouring the solution B into the solution A within 5s, continuously stirring for 1 minute,the mixed solution was aged at room temperature for 12 hours. The obtained precipitate was washed with absolute ethanol and deionized water 3 times, centrifuged, dried at 70 ℃ overnight, and the sample was collected.
Example 7
Adding 0.2mmol of Ni (Ac)2·4H2O, 0.2mmol trisodium citrate and 2.0g PVP (molecular weight 40000) were dissolved in 20mL H2Forming a solution A in a mixed solution of O and 10mL of DMSO, and magnetically stirring at a certain speed; 0.2mmol K2Pt(CN)4Dissolved in 10mL of H2O, forming a solution B. Then solution B was slowly poured into solution A over 5s, and after stirring was continued for 1 minute, the mixed solution was aged at room temperature for 24 hours. The obtained precipitate was washed with absolute ethanol and deionized water 3 times, centrifuged, dried at 70 ℃ overnight, and the sample was collected.
Example 8
0.2mmol of K2PtCl40.02mmol of trisodium citrate and 2.0g of PVP (molecular weight 40000) are dissolved in 20mL of H2Forming a solution A in a mixed solution of O and 10mL of DMSO, and magnetically stirring at a certain speed; 0.2mmol K2Ni(CN)4Dissolved in 5mL of H2O, forming a solution B. Then solution B was slowly poured into solution A over 5s, and after stirring was continued for 1 minute, the mixed solution was aged at room temperature for 12 hours. The obtained precipitate was washed with absolute ethanol and deionized water 3 times, centrifuged, dried at 70 ℃ overnight, and the sample was collected.
Example 9
1.5mmol of Ni (Ac)2·4H2O, 1.9mmol trisodium citrate and 2.0g PVP (molecular weight 40000) were dissolved in 30mL H2Forming a solution A in O and 15mL of N, N-dimethylformamide, and magnetically stirring at a certain speed; 1.5mmol K2Ni(CN)4Dissolved in 20mL of H2O, forming a solution B. Then, the solution B was slowly poured into the solution A over 5s, and after stirring was continued for 1 minute, the mixed solution was aged at room temperature for 15 hours. The obtained precipitate was washed with absolute ethanol and deionized water 3 times, centrifuged, dried at 70 ℃ overnight, and the sample was collected.
Example 10
1.5mmol of Co (Ac)2·4H2O, 1.9mmol trisodium citrate and 2.0g PVP (molecular weight 40000) were dissolved in 30mL H2Forming a solution A in O and 15mL of N, N-dimethylformamide, and magnetically stirring at a certain speed; 1.5mmol K2Ni(CN)4Dissolved in 20mL of H2O, forming a solution B. Then solution B was slowly poured into solution A over 5s, and after stirring was continued for 1 minute, the mixed solution was aged at room temperature for 4 hours. The obtained precipitate was washed with absolute ethanol and deionized water 3 times, centrifuged, dried at 70 ℃ overnight, and the sample was collected.
Example 11
1.5mmol of Mn (Ac)2·4H2O, 1.9mmol trisodium citrate and 2.0g PVP (molecular weight 40000) were dissolved in 30mL H2Forming a solution A in O and 15mL of N, N-dimethylformamide, and magnetically stirring at a certain speed; 1.5mmol K2Ni(CN)4Dissolved in 20mL of H2O, forming a solution B. Then, the solution B was slowly poured into the solution A over 5s, and after continuing to stir for 1 minute, the mixed solution was aged at room temperature for 48 hours. The obtained precipitate was washed with absolute ethanol and deionized water 3 times, centrifuged, dried at 70 ℃ overnight, and the sample was collected.
Example 12
1.5mmol of Ni (Ac)2·4H2O, 1.9mmol trisodium citrate and 2.0g PVP (molecular weight 40000) +1.0g SDS in 30mL H2Forming a solution A in O and 15mL of N, N-dimethylformamide, and magnetically stirring at a certain speed; 1.5mmol K2Ni(CN)4Dissolved in 20mL of H2O, forming a solution B. Then, the solution B was slowly poured into the solution A over 5s, and after stirring was continued for 1 minute, the mixed solution was aged at room temperature for 15 hours. The obtained precipitate was washed with absolute ethanol and deionized water 3 times, centrifuged, dried at 70 ℃ overnight, and the sample was collected.
Example 13
1.5mmol of Ni (Ac)2·4H2O, 1.9mmol trisodium citrate and 2.0g SDS dissolved in 30mL H2Forming a solution A in O and 15mL of N, N-dimethylformamide, and magnetically stirring at a certain speed; 1.5mmol K2Ni(CN)4Dissolved in 20mL of H2O, forming a solution B.Then, the solution B was slowly poured into the solution A over 5s, and after stirring was continued for 1 minute, the mixed solution was aged at room temperature for 15 hours. The obtained precipitate was washed with absolute ethanol and deionized water 3 times, centrifuged, dried at 70 ℃ overnight, and the sample was collected.
Example 14
1.5mmol of Ni (Ac)2·4H2O, 1.9mmol trisodium citrate and 3.0g PVP (molecular weight 40000) were dissolved in 30mL H2O and 20mL acetonitrile to form a solution A, and magnetically stirring at a certain speed; 1.5mmol K2Ni(CN)4Dissolved in 20mL of H2O, forming a solution B. Then, the solution B was slowly poured into the solution A over 5s, and after stirring was continued for 1 minute, the mixed solution was aged at room temperature for 12 hours. The obtained precipitate was washed with absolute ethanol and deionized water 3 times, centrifuged, dried at 70 ℃ overnight, and the sample was collected.
Example 15
1.5mmol of Co (Ac)2·4H2O, 1.9mmol trisodium citrate and 3.0g PVP (molecular weight 40000) were dissolved in 30mL H2O and 20mL acetonitrile to form a solution A, and magnetically stirring at a certain speed; 1.5mmol K2Ni(CN)4Dissolved in 20mL of H2O, forming a solution B. Then, the solution B was slowly poured into the solution A over 5s, and after stirring was continued for 1 minute, the mixed solution was aged at room temperature for 12 hours. The obtained precipitate was washed with absolute ethanol and deionized water 3 times, centrifuged, dried at 70 ℃ overnight, and the sample was collected.
EXAMPLE 16 characterization of the products of examples 1-15
(1) Characterization of micro-topography
The morphology and structure of the sample were characterized using a field emission scanning electron microscope (SEM, Nova Nano 450) at 15KV voltage.
(2) Phase characterization
Analyzing the phase of the sample by X-ray diffraction analysis (XRD), wherein the experimental parameters of the instrument are as follows: using a Cu-Ka radiation source at a wavelength λ
Figure BDA0002625019020000071
Test of 40kvThe tube pressure and the test tube flow of 40mA are respectively controlled, the scanning range is 10-80 degrees, and the scanning speed is 20 degrees min-1。
(3) Material structural characterization
The chemical structure information of the sample was characterized using a Fourier transform infrared spectrometer model Thermo Fisher, Nicolet 6700.
Comparative example
The literature reports that: hoffman type coordination polymer Ni (H)2O)x[Ni(CN)4]·yH2The preparation method of the O nanosheet comprises the following steps:
0.4mmol of NiCl. xH2Dissolving O and 0.3mmol trisodium citrate in water to obtain a solution A; 0.4mmol of K2[M′(CN)4]Dissolving in deionized water to obtain solution B; and pouring the B into the A, aging for 12h at room temperature, and centrifugally drying to obtain a sample.
Compared with the invention: the sample obtained by the preparation method has irregular sheet shape in microscopic appearance, rough surface and low yield. According to the invention, the surfactant is additionally added in the preparation process, the reactant proportion is adjusted, and the solvent system of the reaction is tried to be replaced, so that various Hofmann coordination polymer nanosheets with regular appearance, smooth surface and unique structure are obtained.

Claims (6)

1. A preparation method of a Hoffman type coordination polymer nano material is characterized by comprising the following steps:
dissolving a metal M salt, trisodium citrate and a surfactant in a solvent to obtain a mixed solution; will K2[M′(CN)4]Dissolving in deionized water to obtain K2[M′(CN)4]A solution; will K2[M′(CN)4]Adding the solution into the mixed solution, stirring, aging at room temperature for 4-48 h, cleaning, centrifuging and drying the formed precipitate to obtain the Hoffman type coordination polymer nano material;
m in the metal M salt is Pt, Co, Ni or Mn;
the surfactant is selected from one or more of polyvinylpyrrolidone, sodium dodecyl sulfate and dodecyl trimethyl ammonium bromide;
said K2[M′(CN)4]Represents K2Ni(CN)4Or K2Pt(CN)4；
The solvent is deionized water, or the volume ratio of the deionized water to the organic solvent is 1-2: 1, a mixed solvent; the organic solvent is selected from dimethyl sulfoxide, N-dimethylacetamide, dimethyl imidazolidinone, hexamethylphosphoric triamide, N-methylformamide, N-dimethylformamide, acetonitrile or L-cysteine.
2. The method for preparing the hoffman-type coordination polymer nanomaterial of claim 1, wherein the metal M salt, trisodium citrate, and K are2[M′(CN)4]The ratio of the amounts of substances (1): 0.1-1.5: 1.
3. the method for preparing the Hofmann coordination polymer nanomaterial as claimed in claim 1, wherein the mass usage of the surfactant is 1-10 g/mmol based on the amount of the metal M salt.
4. The method for preparing the Hoffman-type coordination polymer nanomaterial of claim 1, wherein the metal M salt is Ni (Ac)2·4H2O、K2PtCl4、Co(Ac)2·4H2O or Mn (Ac)2·4H2O。
5. The method for preparing the Hofmann coordination polymer nanomaterial according to claim 1, wherein the volume usage amount of the solvent is 10-150 mL/mmol based on the amount of the metal M salt.
6. The method for preparing the Hoffman-type coordination polymer nanomaterial of claim 1, wherein K is2[M′(CN)4]The concentration of the solution is 0.02-0.075 mmol/mL.
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