CN117736244A - Pd with octahedral structure 6 (SR) 12 Cluster and preparation method thereof - Google Patents

Pd with octahedral structure 6 (SR) 12 Cluster and preparation method thereof Download PDF

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CN117736244A
CN117736244A CN202211118597.0A CN202211118597A CN117736244A CN 117736244 A CN117736244 A CN 117736244A CN 202211118597 A CN202211118597 A CN 202211118597A CN 117736244 A CN117736244 A CN 117736244A
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cluster
octahedral structure
structure according
preparation
steps
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姚传好
孟常青
严浩
黄维
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Ningbo Research Institute of Northwestern Polytechnical University
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Ningbo Research Institute of Northwestern Polytechnical University
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Abstract

The invention provides a Pd with an octahedral structure 6 (SR) 12 Clusters, pd 6 (SR) 12 The cluster is a palladium cluster protected by a cyclohexanediol ligand, and comprises 6 Pd atoms and 12 cyclohexanediol ligands, wherein 6 Pd atoms form an octahedral core, sulfur atoms in the cyclohexanediol ligands are connected with Pd atoms at the periphery, and each sulfur atom is connected with two Pd atoms. The invention also further discloses Pd 6 (SR) 12 The preparation method of the cluster fills the technical gap of synthesizing Pd clusters with structures other than the annular structure, and has higher popularization value.

Description

Pd with octahedral structure 6 (SR) 12 Cluster and preparation method thereofMethod of
Technical Field
The invention relates to the technical field of nano material preparation, in particular to Pd with an octahedral structure 6 (SR) 12 Clusters and a method for preparing the same.
Background
Metal nanoclusters are aggregates formed of several to several hundred metal atoms, generally less than 3nm in size, and are an emerging nanomaterial. The metal nanoclusters have discrete electronic energy levels and exhibit unique physical and chemical properties such as optics, electricity, catalysis and the like. The ligand-protected metal nanocluster has wide application prospects in multiple fields of biological labeling, catalysis, medicine, photovoltaics, sensing, renewable energy sources and the like. Meanwhile, the physicochemical properties of nanoclusters are closely related to structure and size, which makes nanoclusters have great application potential in some fields.
Ligand-protected metal nanoclusters have been the focus of research, and currently common ligand-protected metal nanoclusters include core-shell structured group IB clusters and cyclic group VIII metal clusters. The palladium in the cyclic cluster has relatively few researches, and the palladium metal cluster has good oxidation resistance, reduction resistance and thermal stability, and excellent electrocatalytic and nonlinear optical properties.
A series of cyclic palladium clusters [ Pd (SR) have been reported 2 ] n (n=4 to 20), however, no Pd cluster having a structure other than a cyclic structure has been synthesized, and there is no report on the production method.
Disclosure of Invention
One of the technical problems to be solved by the invention is to provide Pd with an octahedral structure 6 (SR) 12 Clusters, which are different from the reported cyclic structures, and whose precise structure was obtained by X-ray single crystal diffraction test.
In order to solve the problems, the invention provides a Pd with an octahedral structure 6 (SR) 12 Clusters, pd 6 (SR) 12 The clusters are palladium clusters protected by cyclohexanediol ligand and comprise 6 Pd atoms,12 cyclohexanediol ligands and 6 Pd atoms form an octahedral nucleus, and the sulfur atoms in the cyclohexanediol ligands are connected with Pd atoms at the periphery, and each sulfur atom is connected with two Pd atoms.
As a preferred embodiment, the Pd 6 (SR) 12 The molecular formula of the cluster is Pd 6 (SC 6 H 11 ) 12 Belongs to a triclinic system, and the space group is P-1.
As a preferred embodiment, the Pd 6 (SR) 12 The crystallographic parameters of the clusters were: α=91.025(5),β=107.110(5),γ=104.164(5)。
it is a second object of the present invention to provide Pd having an octahedral structure 6 (SR) 12 The preparation method of the cluster solves the problem that Pd with the octahedral structure does not exist at present 6 (SR) 12 A problem with the cluster preparation method.
To solve the problems, the invention provides the octahedral Pd 6 (SR) 12 A method of preparing clusters comprising the steps of:
and S1, dissolving palladium salt in acetonitrile, and stirring for a period of time to obtain a brown solution A containing palladium ions.
S2, adding cyclohexanediol into the brown solution A in the step S1, and continuing to stir and react for a period of time to obtain a yellow-brown solution B;
s3, adding triethylamine into the yellowish-brown solution B in the step S2, centrifuging and precipitating the product after stirring reaction, and repeatedly washing to remove superfluous mercaptan to obtain yellow precipitate C;
s4, dissolving the yellow precipitate C obtained in the step S3 in an organic solvent, extracting to obtain a red solution, separating by using a thin layer chromatography, extracting the separated and collected product by using the organic solvent, and carrying out single crystal culture to obtain the Pd with the octahedral structure 6 (SR) 12 Clusters.
In a preferred embodiment, in the step S1, the palladium salt is palladium acetate trimer.
In the preferred scheme, in the step S1, the stirring speed is 600-1000 r/min, and the stirring reaction time is 15-20 min.
Preferably, in the step S2, the molar ratio of the cyclohexyl mercaptan to the palladium ion is (1-12): 1.
in a preferred embodiment, in the step S2, the stirring rate of the stirring reaction is 600-1000 r/min, and the stirring reaction time is 15-20 min.
In a preferred embodiment, in the step S3, the molar ratio of the triethylamine to the palladium ion is (1 to 8): 1.
in the preferred scheme, in the step S3, the stirring speed is 600-1000 r/min, and the stirring reaction time is 6-10 h.
In a preferable embodiment, in the step S3, acetonitrile is used for centrifugal washing for 1 to 5 times, and the centrifugal rotation speed is 10000rpm/min.
In a preferred embodiment, in the step S4, the organic solvent is dichloromethane and/or toluene, respectively.
Compared with the prior annular Pd cluster, the invention has the following advantages:
(1) Cyclic Pd as compared with the prior reported Pd 6 The Pd is compared with the cluster 6 (SR) 12 Clusters have a unique octahedral structure.
(2) Pd of octahedral structure 6 (SR) 12 UV-vis absorption spectra of clusters and cyclic Pd reported previously 6 The clusters have obvious differences, and the nuclear structure has great influence on the optical property and the electronic structure of the nanoclusters, and has great significance for researching the influence of structural isomers on the optical property.
(3) The palladium cluster has good electrocatalytic performance, and can catalyze hydrogen and oxygen to directly synthesize hydrogen peroxide, and Pd with octahedral structure 6 (SR) 12 The study of clusters has helped to understand in depth the relationship between structure and properties.
Drawings
FIG. 1 is Pd of octahedral structure 6 (SR) 12 Analysis chart of crystal structure
Detailed Description
The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a Pd with an octahedral structure 6 (SR) 12 Clusters, pd 6 (SR) 12 The cluster is a palladium cluster protected by a cyclohexanediol ligand, and comprises 6 Pd atoms and 12 cyclohexanediol ligands, wherein 6 Pd atoms form an octahedral core, sulfur atoms in the cyclohexanediol ligands are connected with Pd atoms at the periphery, and each sulfur atom is connected with two Pd atoms.
Preferably, the Pd 6 (SR) 12 The molecular formula of the cluster is Pd 6 (SC 6 H 11 ) 12 Belongs to a triclinic system, and the space group is P-1.
Preferably, the Pd 6 (SR) 12 The crystallographic parameters of the clusters were: α=91.025(5),β=107.110(5),γ=104.164(5)。
the invention provides the octahedral Pd 6 (SR) 12 A method of preparing clusters comprising the steps of:
and S1, dissolving palladium salt in acetonitrile, and stirring for a period of time to obtain a brown solution A containing palladium ions.
S2, adding cyclohexanediol into the brown solution A in the step S1, and continuing to stir and react for a period of time to obtain a yellow-brown solution B;
s3, adding triethylamine into the yellowish-brown solution B in the step S2, centrifuging and precipitating the product after stirring reaction, and repeatedly washing to remove superfluous mercaptan to obtain yellow precipitate C;
s4, dissolving the yellow precipitate C obtained in the step S3 in an organic solvent, extracting to obtain a red solution, separating by using a thin layer chromatography, extracting the separated and collected product by using the organic solvent, and carrying out single crystal culture to obtain the Pd with the octahedral structure 6 (SR) 12 Clusters.
Preferably, in the step S1, the palladium salt is palladium acetate trimer.
Preferably, in the step S1, the stirring speed is 600-1000 r/min, and the stirring reaction time is 15-20 min.
Preferably, in the step S2, the molar ratio of the cyclohexyl mercaptan to the palladium ion is (1-12): 1.
preferably, in the step S2, the stirring rate of the stirring reaction is 600-1000 r/min, and the stirring reaction time is 15-20 min.
Preferably, in the step S3, the molar ratio of the triethylamine to the palladium ion is (1 to 8): 1.
preferably, in the step S3, the stirring speed is 600-1000 r/min, and the stirring reaction time is 6-10 h.
Preferably, in the step S3, acetonitrile is adopted for centrifugal cleaning for 1 to 5 times, and the centrifugal rotation speed is 10000rpm/min.
Preferably, in the step S4, the organic solvent is dichloromethane and/or toluene, respectively.
The technical scheme of the invention is developed and described by combining specific actual data:
example 1:
s1: into a 50 mL single neck round bottom flask was added 10mL acetonitrile solvent at room temperature, 33mg of palladium acetate trimer was added and vigorously stirred at 600rpm for 15min to dissolve the palladium acetate trimer.
S2: 100uL of cyclohexyl mercaptan is added into the solution after the reaction in the step S1, a large amount of brown yellow flocculent precipitate rapidly appears in the solution, and stirring is continued for 15min at 600 rpm.
S3: 100uL of triethylamine solution was added to the solution after the reaction in step S2, and the reaction was continued at room temperature for 6 hours. After the reaction is finished, the product is centrifugally precipitated and repeatedly washed by acetonitrile to remove excessive mercaptan, unreacted precursor and other impurities.
S4: drying the reaction product obtained in the step S3, extracting with dichloromethane solution to obtain red solution, separating with thin layer chromatography, extracting the separated and collected product with organic solvent, and growing yellow transparent monocrystal by gas phase diffusion to obtain octahedral Pd 6 (SR) 12 Clusters.
Example 2:
s1: into a 50 mL single neck round bottom flask was added 10mL acetonitrile solvent at room temperature, 100mg of palladium acetate trimer was added and vigorously stirred at 600rpm for 15min to dissolve the palladium acetate trimer.
S2: 200uL of cyclohexyl mercaptan is added into the solution after the reaction in the step S1, a large amount of brown yellow flocculent precipitate rapidly appears in the solution, and stirring is continued for 15min at 600 rpm.
S3: 100uL of triethylamine solution was added to the solution after the reaction in step S2, and the reaction was continued at room temperature for 6 hours. After the reaction is finished, the product is centrifugally precipitated and repeatedly washed by acetonitrile to remove excessive mercaptan, unreacted precursor and other impurities.
S4: drying the reaction product obtained in the step S3, extracting with dichloromethane solution to obtain red solution, separating with thin layer chromatography, extracting the separated and collected product with organic solvent, and growing yellow transparent monocrystal by gas phase diffusion to obtain octahedral Pd 6 (SR) 12 Clusters.
Example 3:
s1: into a 50 mL single neck round bottom flask was added 10mL acetonitrile solvent at room temperature, 67mg of palladium acetate trimer was added and vigorously stirred at 600rpm for 15min to dissolve the palladium acetate trimer.
S2: 400uL of cyclohexyl mercaptan is added into the solution after the reaction in the step S1, a large amount of brown yellow flocculent precipitate rapidly appears in the solution, and stirring is continued for 15min at 600 rpm.
S3: 100uL of triethylamine solution was added to the solution after the reaction in step S2, and the reaction was continued at room temperature for 6 hours. After the reaction is finished, the product is centrifugally precipitated and repeatedly washed by acetonitrile to remove excessive mercaptan, unreacted precursor and other impurities.
S4: drying the reaction product obtained in the step S3, extracting with dichloromethane solution to obtain red solution, separating with thin layer chromatography, extracting the separated and collected product with organic solvent, and growing yellow transparent monocrystal by gas phase diffusion to obtain octahedral Pd 6 (SR) 12 Clusters.
Example 4:
s1: into a 50 mL single neck round bottom flask was added 10mL acetonitrile solvent at room temperature, 67mg of palladium acetate trimer was added and vigorously stirred at 600rpm for 15min to dissolve the palladium acetate trimer.
S2: 200uL of cyclohexyl mercaptan is added into the solution after the reaction in the step S1, a large amount of brown yellow flocculent precipitate rapidly appears in the solution, and stirring is continued for 15min at 600 rpm.
S3: 200uL of triethylamine solution was added to the solution after the reaction in step S2, and the reaction was continued at room temperature for 6 hours. After the reaction is finished, the product is centrifugally precipitated and repeatedly washed by acetonitrile to remove excessive mercaptan, unreacted precursor and other impurities.
S4: drying the reaction product obtained in the step S3, extracting with dichloromethane solution to obtain red solution, separating with thin layer chromatography, extracting the separated and collected product with organic solvent, and growing yellow transparent monocrystal by gas phase diffusion to obtain octahedral Pd 6 (SR) 12 Clusters.
Octahedral Pd prepared in example 1, example 2, example 3, and example 4 6 (SR) 12 The crystal structure of the clusters is shown in fig. 1. As can be seen from fig. 1, the Pd 6 (SR) 12 The cluster is a palladium cluster protected by a cyclohexanediol ligand, and comprises 6 Pd atoms, 12 cyclohexanediol ligands, 6 Pd atoms form an octahedral nucleus, sulfur atoms in the cyclohexanediol ligands are peripherally connected with the Pd atoms, and eachThe sulfur atom connects two Pd atoms.
The crystal data of the produced crystals of example 1 are shown in table 1 below:
table 1: octahedral Pd 6 (SR) 12 Crystal data of clusters
While the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.

Claims (12)

1. Pd with octahedral structure 6 (SR) 12 A cluster, characterized in that: the Pd is 6 (SR) 12 The cluster is a palladium cluster protected by a cyclohexanediol ligand, and comprises 6 Pd atoms and 12 cyclohexanediol ligands, wherein 6 Pd atoms form an octahedral core, sulfur atoms in the cyclohexanediol ligands are connected with Pd atoms at the periphery, and each sulfur atom is connected with two Pd atoms.
2. Pd of octahedral structure according to claim 1 6 (SR) 12 A cluster, characterized in that: the Pd is 6 (SR) 12 The molecular formula of the cluster is Pd 6 (SC 6 H 11 ) 12 Belongs to a triclinic system, and the space group is P-1.
3. Pd of octahedral structure according to claim 2 6 (SR) 12 Clusters, characterized in thatPd (Pd) 6 (SR) 12 The crystallographic parameters of the clusters were: α=91.025(5),β=107.110(5),γ=104.164(5)。
4. a Pd of octahedral structure according to any one of claims 1-3 6 (SR) 12 A method of preparing clusters, comprising the steps of:
s1, dissolving palladium salt in acetonitrile, and stirring for a period of time to obtain brown solution A containing palladium ions;
s2, adding cyclohexanediol into the brown solution A in the step S1, and continuing to stir and react for a period of time to obtain a yellow-brown solution B;
s3, adding triethylamine into the yellowish-brown solution B in the step S2, centrifuging and precipitating the product after stirring reaction, and repeatedly washing to remove superfluous mercaptan to obtain yellow precipitate C;
s4, dissolving the yellow precipitate C obtained in the step S3 in an organic solvent, extracting to obtain a red solution, separating by using a thin layer chromatography, extracting the separated and collected product by using the organic solvent, and carrying out single crystal culture to obtain the Pd with the octahedral structure 6 (SR) 12 Clusters.
5. Pd of octahedral structure according to claim 4 6 (SR) 12 The preparation method of the cluster is characterized by comprising the following steps: in the step S1, the palladium salt is palladium acetate trimer.
6. Pd of octahedral structure according to claim 4 6 (SR) 12 The preparation method of the cluster is characterized by comprising the following steps: in the step S1, the stirring speed is 600-1000 r/min, and the stirring reaction time is 15-20 min.
7. Pd of octahedral structure according to claim 4 6 (SR) 12 The preparation method of the cluster is characterized by comprising the following steps: in the step S2, the molar ratio of the cyclohexyl mercaptan to the palladium ions is (1-12): 1.
8. pd of octahedral structure according to claim 4 6 (SR) 12 The preparation method of the cluster is characterized by comprising the following steps: in the step S2, the stirring speed of the stirring reaction is 600-1000 r/min, and the stirring reaction time is 15-20 min.
9. Pd of octahedral structure according to claim 4 6 (SR) 12 The preparation method of the cluster is characterized by comprising the following steps: in the step S3, the mol ratio of the triethylamine to the palladium ions is (1-8): 1.
10. pd of octahedral structure according to claim 4 6 (SR) 12 The preparation method of the cluster is characterized by comprising the following steps: in the step S3, the stirring speed is 600-1000 r/min, and the stirring reaction time is 6-10 h.
11. Pd of octahedral structure according to claim 4 6 (SR) 12 The preparation method of the cluster is characterized by comprising the following steps: in the step S3, acetonitrile is adopted for centrifugal cleaning for 1 to 5 times, and the centrifugal rotating speed is 10000rpm/min.
12. Pd of octahedral structure according to claim 4 6 (SR) 12 The preparation method of the cluster is characterized by comprising the following steps: in the step S4, the organic solvent is dichloromethane and/or toluene, respectively.
CN202211118597.0A 2022-09-13 2022-09-13 Pd with octahedral structure 6 (SR) 12 Cluster and preparation method thereof Pending CN117736244A (en)

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