CN113732294A - Method for cheap large-scale synthesis of metal clusters through molten salt - Google Patents
Method for cheap large-scale synthesis of metal clusters through molten salt Download PDFInfo
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- CN113732294A CN113732294A CN202111128105.1A CN202111128105A CN113732294A CN 113732294 A CN113732294 A CN 113732294A CN 202111128105 A CN202111128105 A CN 202111128105A CN 113732294 A CN113732294 A CN 113732294A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F2009/065—Melting inside a liquid, e.g. making spherical balls
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Abstract
The invention relates to a method for synthesizing metal clusters through molten salt at low cost on a large scale, which comprises the following steps: s1, providing molten salt and removing water, wherein the molten salt is inorganic salt of single salt or multi-element mixed salt; s2, adding the pure metal material into the molten salt to perform a dissolution reaction; s3, pouring out at high temperature and cooling to obtain the solid salt containing the metal clusters. According to the molten salt method, metal is put into the molten salt, the molten salt is poured out after a certain time, and the one-step one-pot method is adopted, so that the synthesis method is simple and the operation is very convenient; the environment affinity material melting inorganic salt is used as a reaction solvent, has good environment affinity and basically has no toxicity and harm to human bodies, and is suitable for industrial scale-up production; the metal with lower cost is used as the raw material, so that the defect of high cost of the conventional synthesis method is overcome; the metal cluster molecules are confirmed to be synthesized through the characterization of the spectroscopy and the electron microscope, and a large amount of the metal cluster molecules can be synthesized.
Description
Technical Field
The present invention relates to a metal cluster, and more particularly, to a method for inexpensively synthesizing a metal cluster on a large scale by molten salt.
Background
The metal cluster is a polynuclear nanomaterial with a certain atomic composition and chemical structure and a certain size, which is composed of several or hundreds of atoms. It is popular with material scientists because of its excellent catalytic, photoelectric and biological application properties. Because the metal cluster is easy to polymerize in the production process, the macro preparation of the pure metal cluster is difficult to realize by the traditional techniques for cluster structure research, such as laser ablation, magnetron sputtering and the like, the existing metal cluster synthesis method generally adopts organic ligand protection, and uses metal compounds to synthesize the metal cluster by ligand protection through a water system or an organic system, so that the synthesis method has high cost and complex operation, has certain danger when using a strong reducing agent to carry out reduction reaction, and the synthesized metal cluster basically has no catalytic activity under the ligand protection.
Generally, a metal crystal has very high lattice energy, good ductility and thermal stability, a traditional method for converting metal into a cluster structure with sub-nanometer size dispersion needs to adopt very extreme experimental means, such as laser ablation or magnetron sputtering to generate high-temperature metal plasma, then a rapid cooling technology is used for generating gas-phase cluster ions, and surface deposition is carried out in an ultrahigh vacuum environment, and the generated trace metal cluster is mainly used for microstructure research. Early research focuses on finding cluster structures with special stability and structure-activity relationship of the cluster structures as model systems in catalytic application, and international topic groups try to apply the two methods to macro preparation of clusters, but metal clusters generated by laser ablation or magnetron sputtering are easy to polymerize, so the synthesis methods are still limited in research stages of laboratory scale, and no report is provided about industrial production of the macro metal clusters. In the biological field, the ligand-protected metal clusters can be used as biological markers, and certain clusters have special photoluminescence effects and can be used for cell marking and the like. The performance of the metal cluster is very excellent, and the metal cluster has great development potential in the fields of industry, medicine and the like, researchers are dedicated to developing a synthesis method of the metal cluster, and mass synthesis of the metal cluster is a common target of cluster scientists.
At present, besides the above-mentioned method for producing trace metal clusters under extreme physical conditions, there are several chemical synthesis methods for preparing ligand-protected metal clusters, one is a reduction growth method, which specifically comprises dispersing metal oxides or metal salts in water or an organic solvent, after the dispersion is completed, introducing reducing gases such as carbon monoxide and hydrogen or adding reducing agents such as sodium borohydride and sodium cyanoborohydride to reduce metal ions into zero-valent atoms, collecting and generating clusters in the solvent, dispersing in the solvent, usually adding some ligand molecules in the solvent to make the metal clusters protected by ligands and stably exist, and then separating to obtain specific metal clusters; secondly, a seed growth method is adopted, the synthesized small-sized metal clusters are added into a solvent to serve as a core, the reducing substance is also added, so that metal ions in the solvent grow into metal clusters with larger sizes on the added small metal clusters, and ligand molecules are also required to be added to protect the large-sized metal clusters; and thirdly, a ligand exchange method, wherein the metal clusters of different ligands are synthesized by exchanging ligands at the periphery of the metal clusters.
The defects of the prior art mainly include technical limitation, high synthesis price, complex operation, incapability of industrial amplification and the like. The following describes these disadvantages.
Firstly, the price is high, the laser source or magnetron sputtering source adopted by the physical method cools the metal after the plasma gasification process, the energy consumption is very high, the generated metal clusters are easy to polymerize, the size dispersion degree of the clusters is large, and the regulation and control are difficult. The chemical synthesis of metal clusters mainly uses metal salts or oxides, and takes the gold cluster which is most studied by researchers as an example, the raw material of the gold cluster is oftenCompounds using gold, e.g. chloroauric acid (HAuCl)4) The price of the gold is 8-20 times of that of gold (different purities and prices) and the highest gold content capable of being utilized is only 59%. And the existing synthesis methods generally use expensive organic solvents and require the use of reducing agents. Compared with the metal cluster synthesized by a molten salt method and pure gold, the cost of the raw material is 50 to 100 times higher.
Secondly, the method has the defect of complex operation, the method for physically generating the metal clusters needs to operate and control precise instruments and equipment, for example, the metal clusters are generated by magnetron sputtering, a complex multistage vacuum differential system and a precise time sequence control system need to be designed in the whole process, and extremely high requirements are imposed on the operating environment and workers. The chemical synthesis clustering method is not a one-step method, generally comprises several to ten or more operation steps, and the steps are very complicated, each step needs to be accurately finished by an operator, and otherwise, the synthesis fails. In addition, chemical synthesis also uses reducing gases such as carbon monoxide, hydrogen or reducing substances such as sodium borohydride and sodium cyanoborohydride, all of which have certain dangers that make them more demanding to handle.
Finally, the method has the defect that the industrial scale-up cannot be carried out, the two methods of laser ablation and magnetron sputtering are used for microstructure research of clusters from the first appearance, and the industrial scale-up production cannot be realized at all by the existing physical design scheme. The existing chemical synthesis method has too strict operation requirements, various reagents used at the same time are not lack of toxic and dangerous organic reagents, and milligram-level synthesis can be carried out in a laboratory, but the method is not suitable for scale-up production in industry, and firstly, the production pollution is overlarge; secondly, the harm to human body is large.
Disclosure of Invention
In order to solve the problems of high price and the like in the prior art, the invention provides a method for synthesizing metal clusters on a large scale at low cost by molten salt.
The method for synthesizing the metal clusters through the molten salt at low cost and large scale comprises the following steps: s1, providing molten salt and removing water, wherein the molten salt is inorganic salt of single salt or multi-element mixed salt; s2, adding the pure metal material into the molten salt to perform a dissolution reaction; s3, pouring out at high temperature and cooling to obtain the solid salt containing the metal clusters.
According to the method for synthesizing the metal clusters on a large scale at low cost by the molten salt, the pure metal material is used as a raw material, the molten salt is used as a solvent, the metal clusters are synthesized by utilizing the dissolving-dispersing process of the metal in the molten salt, namely, the metal is directly uniformly dispersed in the molten salt in the form of clusters, so that the one-step synthesis is realized. The size of the generated metal cluster can be regulated and controlled by selecting a metal material with high solubility in the molten salt, or changing the formula of the molten salt, or controlling the heating temperature and the cooling speed, so that a brand-new macro preparation method of the metal cluster with non-ligand protection and controllable size is provided.
A common method for synthesizing metal clusters is generally a method of synthesizing metal clusters in an aqueous system or an organic system, in which metal ions are generally first separated in a solvent system, and then the metal ions are reduced to metal by using a reducing gas or a reducing agent, so that the metal grows into metal clusters in the solvent, and the metal clusters are separated and utilized in a separation process. The method uses molten inorganic salt as a solvent and a reaction system, uses pure metal as a raw material, directly adds the pure metal into the molten salt, directly dissolves the pure metal in the molten salt and disperses the pure metal in a cluster form, quickly cools high-temperature salt into solid salt to preserve the cluster state in the molten salt, and separates or directly utilizes the metal clusters in the solid salt.
Preferably, the molten salt is a chloride, fluoride, bromide, iodide, nitrate or sulfate salt. In a preferred embodiment, the molten salt is LiCl-KCl eutectic molten salt or NaCl-KCl eutectic molten salt or LiBr salt. It should be understood that the size of the metal clusters formed in different molten salts varies.
Preferably, the pure metal material is chromium, iron, nickel, cobalt, manganese, titanium, copper, silver, gold, platinum or palladium.
Preferably, the pure metal material is a metal block, a metal particle or a metal powder. It is to be understood that any form of metal is used as the starting material.
Preferably, the metal clusters are pure metal clusters or alloy type metal clusters.
Preferably, step S1 includes: the molten salt is heated at 120 deg.C (below melting point and above 100 deg.C) for 3 hr or more to remove water. Thereby preventing the generation of acid or oxide after the hydrolysis of water from causing the disadvantage of the subsequent cluster synthesis.
Preferably, step S2 includes: the molten salt is heated to a higher temperature to melt (generally above 700 ℃), and the pure metal material is added into the molten salt at a high temperature and reacts with the molten salt. Specifically, the molten salt is heated to a high temperature to melt and remain molten, and the pure metal material is added to the molten salt to continue heating and maintain the molten state of the molten salt so that the metal is stably dissolved in the molten salt in the form of clusters.
Preferably, step S2 is performed in a crucible. The material of the crucible includes, but is not limited to, graphite, quartz, nickel, platinum, stainless steel, copper, corundum, or inorganic ceramic materials. It will be appreciated that the material of the crucible itself is resistant to high temperatures and does not react with the molten salt and the metal. It should be noted that, if the conductive crucible is used, clusters will precipitate and adhere to the crucible wall at the interface of the molten salt, the crucible and the gas phase, and the metal clusters can be directly applied accordingly.
Preferably, the molten salt is poured from the crucible into a normal-temperature container to be rapidly cooled to be solid after the molten salt is determined to be saturated in the amount of the metal dissolved in the molten salt by dipping the reaction system with an inert bar and performing a composition test.
Preferably, the reaction time of step S2 is greater than one day. It is to be understood that, in general, the longer the reaction time, the larger the amount of the produced, the reaction time of more than one day is not constant, and the metal cluster can be synthesized also in less than one day.
Preferably, step S3 includes: directly pouring the high-temperature molten salt into a high-temperature resistant container, and rapidly cooling the molten salt into solid salt (for storage and standby), wherein the solid salt contains corresponding metal clusters. Wherein, the high temperature resistant container is quartz, corundum, stainless steel, nickel, etc.
Preferably, the metal clusters are directly utilized in the solid salt. In a preferred embodiment, the solid salt is directly subjected to the corresponding catalytic reaction.
Preferably, the metal clusters are separated and purified from the solid salt.
Preferably, the resulting metal cluster is subjected to separation purification by dissolution-extraction, electrophoresis or column separation. In a preferred embodiment, the metal clusters are separated and purified by n-decane extraction.
According to the molten salt method, the metal clusters are synthesized by using high-temperature molten salt and metal, and the metal is only required to be put into the molten salt and poured out after waiting for a certain time, so that the one-step 'one-pot' method is simple in synthesis method and very convenient to operate; the fused inorganic salt of the environment affinity material is used as a reaction solvent, has good environment affinity, basically has no toxicity to human bodies, is suitable for industrial scale-up production, and overcomes the defects of toxic and dangerous reagents used in the traditional synthetic method; the metal with lower cost is used as the raw material, so that the defect of high cost of the conventional synthesis method is overcome; the metal cluster molecules are confirmed to be synthesized through the characterization of the spectroscopy and the electron microscope, and a large amount of the metal cluster molecules can be synthesized. In a word, the method breaks through the defects and limitations of complex operation, high cost, no industrial application value and the like of the traditional synthetic method, expands the synthetic method from a water system and an organic system to a molten inorganic salt system, and emphasizes that the most important difference of the molten salt method for synthesizing the metal clusters and the traditional chemical synthesis is that the metal clusters are different in existing forms, and the pure metal clusters which are prepared by the molten salt method and have high non-ligand protection activity have great industrial application potential. Its advantage mainly lies in: (1) the compatibility is environment-friendly, and inorganic salt is used as a solvent system in the synthesis process, so that the synthetic method is non-toxic and harmless; (2) the operation is simple, the metal is placed in the molten salt for reaction only after the salt is heated to the melting temperature, and the metal is directly poured out for use after the reaction is finished; (3) the synthesized clusters are coated by solid salt, so that air is isolated, and the synthesized clusters are easy to store; (4) the application is wide: the cluster in the salt can be extracted by an organic reagent, the cluster is dispersed in the organic reagent for use, or the synthesized cluster-containing solid salt can be directly dissolved in water for use in a water system, and simultaneously, the solid salt can be smashed into powder for direct use.
Drawings
FIG. 1 shows CuK-edge EXAFS data for liquid LiCl-KCl-Cu (A), solid LiCl-KCl-Cu (B), and CuCl according to example 1 of the present invention;
FIG. 2 shows [ Cu ] in LiCl-KCl-Cu sample according to example 1 of the present invention21]7+A cluster model;
FIG. 3 shows LiCl-KCl-Cu nordecanol extract according to example 1 of the present invention;
FIG. 4 is an SXAS spectrum of the LiCl-KCl-Cu nordecanol extract of FIG. 3;
FIG. 5 shows Cu in LiCl-KCl-Cu according to example 1 of the present inventionxThe STEM test result of (1);
FIG. 6 shows TEM test results of crucible-attached copper according to example 1 of the present invention;
FIG. 7 is a high temperature UV-visible absorption spectrum of Fe-dissolved LiCl-KCl salt according to example 2 of the present invention;
FIG. 8 shows the measurement results of EXAFS of NaCl-KCl-Fe according to example 2 of the present invention;
FIG. 9 is a schematic diagram of a model of Fe cluster resolved from FIG. 8;
FIG. 10 shows a titanium block according to example 3 of the present invention before dissolution;
FIG. 11 shows a dissolved titanium mass according to example 3 of the present invention;
figure 12 shows a LiBr salt containing Ti according to example 3 of the present invention;
fig. 13 shows Ti cluster powder according to example 3 of the present invention.
Detailed Description
The preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
Example 1
Putting the LiCl-KCl eutectic molten salt into a graphite crucible, heating at 120 ℃ for more than 3 hours to remove water in the salt, and after the water removal is finished, heating the LiCl-KCl eutectic molten salt to a high temperature for melting and keeping the LiCl-KCl eutectic molten salt in a molten state; putting the copper block into molten salt, continuously heating to 700 ℃ and maintaining for more than 1 day to ensure that the copper is stably dissolved in the molten salt in a cluster form; directly pouring the high-temperature molten salt into a quartz container to rapidly cool the molten salt into solid, wherein the solid salt contains corresponding copper clusters.
The high temperature in situ EXAFS measurements were performed on the Cu-dissolved LiCl-KCl salt heated to the molten state, as shown in figure 1, mainly to determine the chemical bonds present therein, and the results showed that mainly Cu-Cu bonds therein proved to be indeed Cu clusters.
The results of the EXAFS measurement of the Cu-dissolved LiCl-KCl salt were analyzed, and the Cu cluster model obtained is shown in FIG. 2, from which it was found that the cluster mainly contains 21 copper atoms (i.e., Cu) in the high-temperature molten salt21 7+Structure) is present.
The obtained solid salt was subjected to dissolution-extraction, and gold yellow copper cluster solution (i.e., LiCl-KCl-Cu aqueous solution) was obtained by extraction using n-decanone solvent, as shown in fig. 3, and the extraction result showed that the copper clusters could be easily separated.
The extraction solution was subjected to a small angle scattering measurement, as shown in FIG. 4, indicating that the Cu cluster size in the extraction solution was small. The results show that Cu is in the solidified molten saltxHas a size distribution of between 0.75 and 3 nm.
The extract was subjected to STEM measurement and the solid salt extract was further analyzed, and as shown in FIG. 5, a clear picture of copper clusters was observed.
The TEM was used to analyze the molten salt, the copper clusters precipitated at the interface between the crucible and the gas phase interface, as shown in fig. 6, which proves that the copper precipitated at the crucible-molten salt interface consisted of copper clusters.
Example 2
Putting the NaCl-KCl eutectic molten salt into a graphite crucible, heating at 120 ℃ for more than 3 hours to remove water in the salt, and after the water removal is finished, heating the LiCl-KCl eutectic molten salt to a high temperature for melting and keeping the LiCl-KCl eutectic molten salt in a molten state; putting the iron blocks into the molten salt, continuously heating to 800 ℃ and maintaining for more than 1 day to ensure that the iron is stably dissolved in the molten salt in a cluster form; directly pouring the high-temperature molten salt into a quartz container to rapidly cool the molten salt into solid, wherein corresponding iron clusters exist in the solid salt.
ICP-AES show in the salt bulk phaseThe Fe content is high, but the dissolved Cr and Fe are colorless in the molten salt. FIG. 7 shows the high temperature UV-visible absorption spectra of LiCl-KCl salt with Fe dissolved, indicating that the dissolved Fe is not Fe in the molten salt2+/Fe3+I.e. not oxidised to the ionic state into the molten salt, in combination with ICP-AES data, it was demonstrated that Fe dissolved into the molten salt in a lower valence state.
To determine whether clusters are generated, an EXAFS test is performed to determine their valence and form of existence. For example, FIG. 8 shows the K-edge absorption result of EXAFS measurement on NaCl-KCl-Fe, and FIG. 9 shows the XANES experiment result on NaCl-KCl-Fe, which resolves the structural model of Fe cluster in NaCl-KCl. In the K-edge absorption experiment results, the experimental curve is compared with Fe/FeO/Fe2O3And Fe3C, comparing the standard substance, finding that the standard substance is best matched with the Fe curve, and determining that the standard substance is zero-valent; the results of XANES experiments show that the bonds are long and have Fe-Fe bonds and exist in the form of clusters.
Example 3
Putting LiBr salt into a nickel crucible, heating at 120 ℃ for more than 3 hours to remove water in the salt, heating the LiBr salt to high temperature to melt after the water removal is finished, and keeping the LiBr salt molten; putting the titanium block into the molten salt, continuously heating to 800 ℃ and maintaining for more than 1 day to ensure that iron is stably dissolved in the molten salt in a cluster form; directly pouring the high-temperature molten salt into a quartz container to rapidly cool the molten salt into solid, wherein the solid salt contains corresponding metal clusters.
Fig. 10 shows the mirror-surface titanium block before dissolution, and fig. 11 shows the titanium block after dissolution, from which it is known that a large amount of titanium has been dissolved into the molten salt LiBr.
The solid LiBr salt containing Ti is shown in figure 12. The titanium-containing LiBr salt was washed with water and suction-filtered to obtain black titanium cluster powder as shown in fig. 13.
The above embodiments are merely preferred embodiments of the present invention, which are not intended to limit the scope of the present invention, and various changes may be made in the above embodiments of the present invention. All simple and equivalent changes and modifications made according to the claims and the content of the specification of the present application fall within the scope of the claims of the present patent application. The invention has not been described in detail in order to avoid obscuring the invention.
Claims (10)
1. A method for synthesizing metal clusters inexpensively on a large scale by molten salt, characterized by comprising the steps of:
s1, providing molten salt and removing water, wherein the molten salt is inorganic salt of single salt or multi-element mixed salt;
s2, adding the pure metal material into the molten salt to perform a dissolution reaction;
s3, pouring out at high temperature and cooling to obtain the solid salt containing the metal clusters.
2. The method of claim 1, wherein the molten salt is a chloride, fluoride, bromide, iodide, nitrate, or sulfate salt.
3. The method of claim 1, wherein the pure metallic material is chromium, iron, nickel, cobalt, manganese, titanium, copper, silver, gold, platinum, or palladium.
4. The method of claim 1, wherein the pure metal material is a metal block, a metal particle, or a metal powder.
5. The method according to claim 1, wherein the metal clusters are pure metal clusters or alloy-type metal clusters.
6. The method according to claim 1, wherein step S1 includes: the molten salt is heated at 120 ℃ for more than 3 hours to remove water in the salt.
7. The method of claim 1, wherein in step S2, the molten salt is heated to a high temperature to melt and remain molten, and the pure metal material is added to the molten salt to continue heating and maintain the molten state of the molten salt so that the metal is stably dissolved in the molten salt in the form of clusters.
8. The method according to claim 1, wherein step S3 includes: directly pouring the high-temperature molten salt into a high-temperature resistant container to rapidly cool the molten salt into solid salt, wherein corresponding metal clusters exist in the solid salt.
9. The method of claim 1, wherein the metal clusters are separated and purified from the solid salt.
10. The method according to claim 9, wherein the obtained metal cluster is subjected to separation purification by dissolution-extraction, electrophoresis or chromatographic column separation.
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