CN111496265B - Reduced noble metal lone atom material stable in solution and preparation method thereof - Google Patents

Reduced noble metal lone atom material stable in solution and preparation method thereof Download PDF

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CN111496265B
CN111496265B CN201910096696.5A CN201910096696A CN111496265B CN 111496265 B CN111496265 B CN 111496265B CN 201910096696 A CN201910096696 A CN 201910096696A CN 111496265 B CN111496265 B CN 111496265B
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张宗超
李会香
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention provides a material of a stable reduction state noble metal lone atom in a solution and a preparation method thereof. Consists of a reduction state noble metal lone atom and a protective agent. And a chain compound containing ether bond groups is used as a protective agent to ensure that a reduction-state noble metal single atom stably exists. The invention adopts chain ether compound as the protective agent for the first time to prepare the noble metal lone atom material in the solution, thereby avoiding the generation of nano particles caused by the accumulation of primary lone atoms in the synthesis process. The reduced lone atoms of the material are different from metal nanoparticles, and can be used in the fields of energy materials, medical synthesis, medical materials, catalyst preparation and the like. And also provides a basic single atom raw material for the synthesis of homogeneous or heterogeneous metal clusters and nano materials with controllable number.

Description

Reduced noble metal lone atom material stable in solution and preparation method thereof
Technical Field
The invention belongs to the field of new materials, and particularly relates to a material which is stable in a solution containing a protective agent and is a reduced noble metal lone atom material.
Background
Precious metals and their alloys are widely used materials in modern industry due to their excellent properties. Due to the characteristics of high-temperature corrosion resistance, high reliability, high precision, long service life and the like, the noble metal is widely applied to the manufacturing of precision instruments for aerospace, navigation industry and military industry, such as spring leaves, capsules, conductive hairsprings, shaft tips and other elements. Meanwhile, the noble metal is widely applied to the preparation of medical materials due to the physiological non-toxicity, good ductility and biocompatibility of the material. Such as amalgam alloy and cast alloy in the dental field, medical gold needle, silver needle and hard needle, electrode material for medical electronic equipment, etc. Furthermore, noble metals possess unique catalytic properties and stability, especially the platinum group metals (iridium, rhodium, palladium and platinum), which are widely used in the fields of petrochemical industry, hydrogen fuel cells, and the like. However, the scarcity of precious metal resources and the laggard manufacturing process technology lead the price of precious metals to be high, and the full utilization of the precious metals in various fields is severely restricted.
The noble metal lone atoms provide wide space for the utilization of noble metals. Maria Flytzani-Stephanopoulos et al (Acc. chem. Res,2014,47,783.) reported the synthesis of Au monatomic materials on a variety of different supports and their successful application to water gas shift reactions. Billow et al (Nature chem.,2011,3,634.) reported the synthesis of Pt monatomic materials on the surface of iron oxide and successfully applied them to the oxidation reaction of carbon monoxide, with a 2-3 fold increase in the conversion frequency of the reaction. However, the monatomic material obtained by the solid surface dispersion method has not only a lot of problems such as low loading amount and instability, but also the noble metal monatomic does not exist in an isolated state due to the interaction between the solid surface and the noble metal monatomic, the noble metal monatomic exists in a state of being bound to the solid surface, the reaction force with oxygen and the like on the carrier is strong, the metal center is not in a complete reduction state (Nature Nanotechnology,2018, 13, 856; Nature Commu.,2019,10,234), and the monatomic material cannot be easily peeled off from the solid surface, and therefore, the monatomic material cannot be used as a raw material for generating and preparing more extensive substances. The reduced noble metal atoms have large freedom of movement in the solution and are easy to aggregate to cause the generation of nano particles, so that the method for dispersing the reduced noble metal atoms in the solution as a medium to obtain the isolated noble metal single atom material is always a great challenge in the field of science and technology. Vinyl pyrrolidone polymers, isopropyl acrylamide polymers, and the like (J.Phys. chem. B,1999,103,3818.; Langmuir 1997,13, 6465.). High molecular polymers are widely applied to synthesis of noble metal materials in solution, however, the high molecular polymers are difficult to prevent noble metal lone atoms in an initial reduction state from aggregating and growing into nanoparticles. Surfactants have also been used for the synthesis of noble metal materials in solution, but are difficult to remove, and the degree of freedom of noble metal atoms encapsulated by the surfactant is limited (patent No. 201611004958.3), and the application characteristics of the materials are affected by the high molecular weight polymer and the surfactant remaining in the materials.
Based on the current research situation, how to overcome the defects that the carrying capacity of the material for preparing the isolated atoms by means of solid surface dispersion is low, the isolated atoms of the initial reduced noble metal are easy to aggregate and grow, the protective agent in the system is difficult to remove and the like is achieved, and therefore the method for effectively preparing the stable material for preparing the isolated atoms of the reduced noble metal has important significance.
The invention discloses a stable reduction state noble metal lone atom material in solution and a preparation method thereof, wherein the material can stably exist in a solvent containing a protecting group. This is in contrast to the organometallic compounds reported in the literature. Marc-Etienne Moret, Bel' n Gil et al describe various types of metal complexes (high oxidation state organization and platinum chemistry. J. CHEM. SOC. DALTON TRANS,1993, 3051. 3057; Inorg. chem.2006,45, 7788. 7798; J.Am. chem. Soc.2011,133, 3582-3591; Angew. chem. int. Ed.2018,57,1-6. such as { [ (C) 6 F 5 ) 3 (tht)Pt]Ag(PPh 3 ) And (tht is tetrahydrothiophene), wherein Pt and Ag are bonded in the form of ions, i.e. Pt (II) and Ag (I), and a ligand containing phosphorus, carbon and the like is arranged around the metal center. Metal Pd atom complex
Figure BDA0001964670880000021
And is structured as
Figure BDA0001964670880000022
In the complex of (1), nitrogen-and carbon-containing ligands are arranged around the metal center to stabilize the structure.
In the metal complex, the valence state of the metal is non-reduction state, and the metal center and the nitrogen, phosphorus or carbon-containing ligand form a metal-carbon bond, a metal-nitrogen or a metal-phosphorus bond. Namely, the reported metal complexes are organometallic compounds. This is in contrast to the one described in this invention, which is a stable metal lone material in solution.
The reduced noble metal lone atom material stable in the solution can be used in the fields of material preparation, industrial catalysis and the like. For example, the reduced Pt alone material can be used in hydrosilylation of unsaturated compounds (hydrosilylation refers to a reaction in which a compound containing Si-H bonds and an unsaturated organic compound undergo an addition reaction to form an organosilicon compound). The reduced Au isolated atomic material can be applied to the oxidation reaction of carbon monoxide under the low temperature condition. In addition, the reduced noble metal atomic material can also be applied to a material coating.
Disclosure of Invention
The invention aims to provide a reduced noble metal lone atom material which is stable in a solution.
The material consists of a reduced noble metal lone atom and a protective agent, wherein the protective agent comprises a chain ether compound.
The noble metal lone atom in the invention is independent, no metal bond is formed between metals, and the chemical valence state of the noble metal is not higher than positive valence and is 0 valence, or the combination of 0 valence and positive valence, and preferably 0 valence. For metals with common valence states without a positive valence, such as Pt, Pd, etc., the ratio of the metal lone atom in the solution with a chemical state of zero valence is at least 30%. For metals with normal valence and containing positive valence, such as silver, the proportion of the metal lone atom in the solution with the chemical state of zero valence is not less than 80%.
The noble metal lone atom comprises one or more than two of platinum group elements and post-platinum group elements, including but not limited to one or more than two of palladium, rhodium, iridium, ruthenium, osmium, platinum and gold.
The noble metal lone atom is a platinum atom or a gold atom.
The protective agent comprises but is not limited to one or more than two compounds with glycol ether structure; including but not limited to one or more than two of compounds with structures of glycol ethers and propylene glycol ethers.
The protective agent comprises but is not limited to one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol diethyl ether and triethylene glycol diethyl ether.
The molar ratio of the noble metal lone atoms to the protective agent is less than or equal to 1:1, preferably in the range from 10 to 10 6 。
The concentration range of the noble metal lone atoms is more than 0 to 1 mol/L.
The concentration range of the noble metal lone atoms is 0.01 to 50 mmol/L.
The components of the material in the preparation process comprise but are not limited to a chain ether compound, a high oxidation state noble metal compound precursor and a reducing agent, or comprise but are not limited to a chain ether compound, a high oxidation state noble metal compound precursor, a reducing agent and water; all the components are fully mixed into a liquid system according to the required proportion, and a stably existing noble metal monoatomic solution can be obtained after reaction.
The preparation process of the material can comprise one or two or three of the following three conditions that the mixed system becomes liquid;
the first method comprises the following steps: the component composition can contain water, the mass concentration range of the water is 0-70%, and the water can be used as a solvent composition;
and the second method comprises the following steps: when the chain ether compound in the component composition contains a protective agent which is liquid at room temperature, the liquid chain ether compound can be used as a solvent composition;
and the third is that: when the reducing agent in the composition of the component contains a reducing agent that is liquid at room temperature, the liquid reducing agent may be used as the solvent composition.
The high oxidation state precious metal compound precursor includes, but is not limited to, one or more of a high oxidation state platinum compound precursor (one or two of bivalence and bivalence), a high oxidation state palladium compound precursor (one or two of bivalence and bivalence), a high oxidation state rhodium compound precursor (positive trivalent), a high oxidation state iridium compound precursor (one or two of trivalence and bivalence), a high oxidation state ruthenium compound precursor (positive trivalent), a high oxidation state osmium compound precursor (one or two or three of bivalence, bivalence and bivalence) or a high oxidation state gold compound precursor (positive trivalent).
The high oxidation state noble metal compound precursor includes, but is not limited to: one or more of chloroauric acid, sodium chloroaurate, potassium chloroaurate, ammonium chloroaurate, chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate, platinous chloride, platinum, potassium chloroplatinate, sodium chloroplatinate, diethylamine platinum chloride, platinum nitrate, 1, 5-cyclooctadiene platinum dichloride, potassium trichloro (ethylene) platinate, dichlorotetraammineplatinum, dinitrile phenyl dichloroplatinum, bis (triphenyl phosphite) platinum dichloride, ammonium tetrachloroplatinate, ammonium chloropalladate, sodium chloropalladate, potassium chloropalladate, ammonium chlororhodate, potassium chlororhodate, chloroiridic acid, sodium chloroiridate, potassium chloroiridate and ammonium chloroiridate.
The reducing agent includes, but is not limited to, one or a mixture of more than two of alcohol compounds, glucose, formic acid, citric acid, tartaric acid, ascorbic acid, hydrazine hydrate or borohydride.
The alcohol compound reducing agent comprises one or a mixture of more than two of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, ethylene glycol and glycerol.
The invention provides a material of a stable reduction state noble metal lone atom in solution. Consists of a reduction state noble metal lone atom and a protective agent. And a chain compound containing ether bond groups is used as a protective agent to ensure that a reduction-state noble metal single atom stably exists. The invention adopts chain ether compound as the protective agent for the first time to prepare the noble metal lone atom material in the solution, thereby avoiding the generation of nano particles caused by the accumulation of primary lone atoms in the synthesis process. The reduced state isolated atom of the material is different from metal nano particles, and can be used in the fields of energy materials, medicine synthesis, medical materials, catalyst preparation and the like. And also provides a basic single atom raw material for the synthesis of homogeneous or heterogeneous metal clusters and nano materials with controllable number.
Drawings
FIG. 1 is a UV-visible spectrum of examples 1,3,4,5, 6.
FIG. 2 shows examples 1,3,4,5 and 6 195 PtNMR spectrum.
FIG. 3 is a UV-visible spectrum of example 2.
FIG. 4 is a UV-visible spectrum of example 7.
FIG. 5 is a transmission electron microscopy analysis chart of high resolution spherical aberration correction scanning in example 9.
Detailed Description
The present invention will be described in further detail below with reference to platinum, gold, and lone atom materials which are stable in solution. The protection sought herein is not to be limited to the specific embodiments described, but only by the claims set forth below.
Example 1
Preparation of platinum single atoms in solution: 67ml of ethylene glycol diethyl ether, 67ml of ethanol, 10.2ml of water and 4.8ml of a chloroplatinic acid solution having a concentration of 0.018mol/L were thoroughly mixed, then the temperature was raised, and the mixture was refluxed by condensation at 75 ℃ for 24 hours to completely reduce chloroplatinic acid. The ethanol and the ethylene glycol diethyl ether in the solution can be removed by a reduced pressure distillation method. By ultraviolet irradiation 195 Pt NMR detection shows that the platinum lone atom material is obtained through synthesis. The UV-Vis absorption spectrum (FIG. 1) shows that: chloroplatinic acid was completely reduced. (Explanation: in the preparation, PtCl was analyzed by an ultraviolet spectrometer 6 2- The absorption intensity of the ion peak was varied with time as shown in FIG. 1. The UV absorption peak at 265nm represents PtCl 6 2- The absorption peak of (1). The intensity of the uv absorption peak gradually decreased to disappear (from top to bottom) with time, indicating that chloroplatinic acid was gradually reduced to complete reduction. 195 The Pt NMR spectrum (fig. 2) shows: reduced platinum lone atoms are formed. (Explanation: K) 2 PtCl 6 Is/are as follows 195 Pt NMR at 0ppm, PtCl 4 2- Peak of-1617 ppm, and Pt alone atom 195 The Pt NMR peak is-2755 ppm, and the large broad peak of the nano-meter shift of the platinum nanoparticles is not detected, namely-35000 ppm to 10000ppm, which indicates that H 2 PtCl 6 Complete reduction and generation of Pt single atoms, and no generation of Pt nano particles. ) After 240h, the analysis was repeated and the results remained unchanged.
Example 2
Preparation of lone atoms in solution: 67ml of ethylene glycol diethyl ether, 67ml of ethanol, 10.2ml of water and 3ml of a chloroauric acid solution with a concentration of 0.0243mol/L were mixed thoroughly, then the temperature was raised, and the mixture was condensed and refluxed at 80 ℃ for 24 hours to completely reduce the chloroauric acid. The UV-Vis absorption spectrum (FIG. 3) shows that: the chloroauric acid was completely reduced. After 240h, the analysis was repeated and the results remained unchanged. (Explanation: during the preparation process, AuCl was analyzed by an ultraviolet spectrometer 4 - Absorption of ion peaksThe intensity of the light received varies with time as shown in FIG. 1. The UV absorption peak at 322nm represents AuCl 4 - Absorption peak of ion. The intensity of the UV absorption peak gradually decreased (from top to bottom) over time, indicating that the chloroauric acid was gradually reduced. The ethanol and the ethylene glycol diethyl ether in the solution can be removed by a reduced pressure distillation method.
Example 3
Preparation of platinum single atoms in solution: 60ml of propylene glycol dimethyl ether, 60ml of ethanol, 10ml of water and 4.8ml of a chloroplatinic acid solution with the concentration of 0.018mol/L are thoroughly mixed, then the temperature is raised, and the mixture is condensed and refluxed at 75 ℃ for 14 hours to completely reduce the chloroplatinic acid. By ultraviolet irradiation 195 Pt NMR detection shows that the platinum lone atom material is obtained by synthesis. The ultraviolet-visible absorption spectrum is the same as that of FIG. 1. (Explanation: in the preparation, PtCl was analyzed by an ultraviolet spectrometer 6 2- The absorption intensity of the ion peak was varied with time as shown in FIG. 1. The UV absorption peak at 265nm represents PtCl 6 2- The absorption peak of (1). The intensity of the uv absorption peak gradually decreased to disappear (from top to bottom) with time, indicating that chloroplatinic acid was gradually reduced to complete reduction. 195 The Pt NMR spectrum is the same as that shown in figure 2. After 240h, the analysis was repeated and the results remained unchanged. (Explanation: K) 2 PtCl 6 Is/are as follows 195 Pt NMR at 0ppm, PtCl 4 2- Peak of-1617 ppm, and Pt alone atom 195 The Pt NMR peak is-2755 ppm, and the large broad peak of the nano-meter shift of the platinum nanoparticles is not detected, namely-35000 ppm to 10000ppm, which indicates that H 2 PtCl 6 Complete reduction and generation of Pt single atoms, and no generation of Pt nano particles. )
Example 4
Preparation of platinum lone atoms in solution: 469ml of ethanol, 6.7ml of ethylene glycol diethyl ether (the mass ratio of the ethanol to the ethylene glycol diethyl ether is 130:1), 0.1ml of water (the mass ratio of the ethanol to the water is 1500:1) and 0.48ml of chloroplatinic acid solution with the concentration of 0.018mol/L (the mass ratio of the ethanol to the Pt is 10) 6 1) fully mixing, then heating and stirring for 600 hours at room temperature to completely reduce chloroplatinic acid. By ultraviolet irradiation 195 Pt NMR detection shows that the platinum lone atom material is obtained through synthesis. The ultraviolet-visible absorption spectrum is the same as that of FIG. 1. (Explanation: in the preparation, PtCl was analyzed by an ultraviolet spectrometer 6 2- The absorption intensity of the ion peak was varied with time as shown in FIG. 1. The UV absorption peak at 265nm represents PtCl 6 2- The absorption peak of (1). The intensity of the uv absorption peak gradually decreased to disappear (from top to bottom) with time, indicating that chloroplatinic acid was gradually reduced to complete reduction. 195 The Pt NMR spectrum is the same as that shown in figure 2. After 240h, the analysis was repeated and the results remained unchanged. (Explanation: K) 2 PtCl 6 Is/are as follows 195 Pt NMR at 0ppm, PtCl 4 2- Peak of-1617 ppm, and Pt alone atom 195 The Pt NMR peak is-2755 ppm, and the large wide peak of the nano-meter displacement of the platinum nano-particles is not detected, namely-35000 ppm to 10000ppm, which indicates that H 2 PtCl 6 Complete reduction and generation of Pt single atoms, and no generation of Pt nanoparticles. )
Example 5
Preparation of platinum single atoms in solution: 7ml of ethanol, 67ml of ethylene glycol diethyl ether (mass ratio of ethanol to ethylene glycol diethyl ether: 0.18:1), 1ml of water (mass ratio of ethanol to water: 0.01:1) and 4.8ml of a chloroplatinic acid solution with a concentration of 0.018mol/L (mass ratio of ethanol to Pt: 10:1) were thoroughly mixed, and then the mixture was heated and stirred at room temperature for 600 hours to completely reduce chloroplatinic acid. By ultraviolet irradiation and 195 pt NMR detection shows that the platinum lone atom material is obtained through synthesis. The ultraviolet-visible absorption spectrum is the same as that of FIG. 1. (Note: in the preparation, PtCl was analyzed by an ultraviolet spectrometer 6 2- The absorption intensity of the ion peak was varied with time as shown in FIG. 1. The UV absorption peak at 265nm represents PtCl 6 2- The absorption peak of (1). Over time, the intensity of this uv absorption peak gradually diminished to disappearance (top to bottom), indicating that chloroplatinic acid was gradually reduced to complete reduction. 195 The Pt NMR spectrum is the same as that shown in figure 2. After 240h, the analysis was repeated and the results remained unchanged. (Explanation: K) 2 PtCl 6 Is/are as follows 195 Pt NMR at 0ppm, PtCl 4 2- Peak of-1617 ppm, and Pt alone atom 195 The Pt NMR peak is-2755 ppm, and the large broad peak of the nano-meter shift of the platinum nanoparticles is not detected, namely-35000 ppm to 10000ppm, which indicates that H 2 PtCl 6 Complete reduction and generation of Pt single atoms, and no generation of Pt nano particles. )
Example 6
Preparation of platinum single atoms in solution: 6.7ml of ethanol, 6.7ml of ethylene glycol diethyl ether, 1ml of water and 4.8ml of a solution of chloroplatinic acid having a concentration of 0.018mol/L were thoroughly mixed, and then the mixture was heated and stirred at room temperature for 600 hours to completely reduce chloroplatinic acid. By ultraviolet irradiation and 195 pt NMR detection shows that the platinum lone atom material is obtained by synthesis. The ultraviolet-visible absorption spectrum is the same as that of FIG. 1. (Explanation: in the preparation, PtCl was analyzed by an ultraviolet spectrometer 6 2- The absorption intensity of the ion peak was varied with time as shown in FIG. 1. The UV absorption peak at 265nm represents PtCl 6 2- The absorption peak of (1). The intensity of the uv absorption peak gradually decreased to disappear (from top to bottom) with time, indicating that chloroplatinic acid was gradually reduced to complete reduction. 195 The Pt NMR spectrum is the same as that shown in fig. 2. After 240h, the analysis was repeated and the results remained unchanged. (Explanation: K) 2 PtCl 6 Is/are as follows 195 Pt NMR at 0ppm, PtCl 4 2- Has a peak of-1617 ppm, and Pt is isolated from atoms 195 The Pt NMR peak is-2755 ppm, and the large wide peak of the nano-meter displacement of the platinum nano-particles is not detected, namely-35000 ppm to 10000ppm, which indicates that H 2 PtCl 6 Complete reduction and generation of Pt single atoms, and no generation of Pt nano particles. )
Example 7
Preparing iridium lone atoms in the solution: 67ml of ethylene glycol diethyl ether, 67ml of ethanol, 10.2ml of water and 3ml of chloroiridic acid solution with the concentration of 0.0243mol/L are fully mixed, then the temperature is increased, and the mixture is condensed and refluxed at 70 ℃ for 8 hours to completely reduce chloroiridic acid. The UV-Vis absorption spectrum (FIG. 4) shows that: the chloroiridic acid is completely reduced. After 240h, the analysis was repeated and the results remained unchanged. (Explanation: the absorption peak in the upper line in the ultraviolet absorption spectrum represents IrCl 6 - Absorption peak of ionAnd the disappearance of the ultraviolet absorption peak indicates that the chloroiridic acid is gradually and completely reduced. )
Example 8
Preparation of lone atoms in solution: 67ml of ethylene glycol diethyl ether, 67ml of ethanol, 10.2ml of water and 3ml of a chloroauric acid solution with a concentration of 0.0243mol/L were mixed thoroughly, then the temperature was raised, and the mixture was condensed and refluxed at 80 ℃ for 24 hours to completely reduce the chloroauric acid. The uv-vis absorption spectrum (fig. 3) shows: the chloroauric acid was completely reduced. After 240h, the analysis was repeated and the results remained unchanged. (Note: UV absorption peak at 322nm represents AuCl) 4 - Absorption peak of ion, during the preparation process, AuCl is analyzed by an ultraviolet spectrometer 4 - The absorption intensity of the ion peak changes with time. As shown in FIG. 1, the intensity of the UV absorption peak gradually decreased (from top to bottom) with time, indicating that chloroauric acid was gradually reduced. The stainless steel sheet (2cm x 3cm) was put into the above-prepared gold-atom solution, and after 2 hours, a stainless steel sheet with a gold-plated surface was obtained.
Example 9
Preparing a gold-lone atom catalyst:
150ml of the lone atom solution prepared in example 8 was taken, 1.7g of titanium oxide was added thereto, and after removal of the solvent, 1% Au _ TiO was obtained 2 In the analysis of high resolution spherical aberration correction scanning transmission electron microscope (fig. 5), it can be seen that Au exists in the form of single atom in the obtained sample.

Claims (15)

1. A stable reduced noble metal lone atom material in solution is characterized in that: the material comprises a reduced noble metal lone atom and a protective agent, or consists of the reduced noble metal lone atom and the protective agent, wherein the protective agent is a chain ether compound, and the protective agent is selected from one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol diethyl ether and triethylene glycol diethyl ether.
2. A reduced noble metal lone atom material stable in solution as claimed in claim 1 wherein: the chemical valence of the noble metal lone atom is not higher than positive valence, and is 0 valence or the mixture of 0 valence and positive valence.
3. A reduced noble metal alone atom material stable in solution as claimed in claim 1 wherein: the noble metal lone atoms comprise one or more than two of platinum group elements and post platinum group elements, and comprise one or more than two of palladium, rhodium, iridium, ruthenium, osmium, platinum and gold.
4. A reduced noble metal alone atom material stable in solution as claimed in claim 1 wherein: the noble metal lone atom is a platinum atom or a gold atom.
5. A reduced noble metal lone atom material stable in solution as claimed in claim 1 wherein: the molar ratio of the noble metal lone atoms to the protective agent is less than or equal to 1: 1.
6. a reduced noble metal lone atom material stable in solution as claimed in claim 1 wherein: the concentration range of the noble metal lone atoms is more than 0 to 1 mol/L.
7. A method for preparing a reduced noble metal lone atom material stabilized in solution as defined in any one of claims 1 to 6, wherein: the components of the material in the preparation process comprise a chain ether compound, a high oxidation state precious metal compound precursor and a reducing agent, or comprise the chain ether compound, the high oxidation state precious metal compound precursor, the reducing agent and water;
all the components are fully mixed into a liquid system according to the required proportion, and a stably existing noble metal monoatomic solution can be obtained after reaction.
8. A method of preparing a reduced noble metal lone atom material stable in solution as claimed in claim 7, wherein:
the preparation process of the material can comprise one or two or three of the following three conditions that the mixed system becomes liquid;
the first method comprises the following steps: the component composition can contain water, the mass concentration range of the water is 0-70%, and the water can be used as a solvent composition;
and the second method comprises the following steps: when the chain ether compound in the component composition contains a protective agent which is liquid at room temperature, the liquid chain ether compound can be used as a solvent composition;
and the third is that: when the reducing agent in the composition of the component (b) contains a reducing agent which is liquid at room temperature, the liquid reducing agent may be used as the solvent composition.
9. A method of preparing a reduced noble metal lone atom material stable in solution according to claim 7, wherein: the noble metal compound precursor in a high oxidation state comprises: one or more of chloroauric acid, sodium chloroaurate, potassium chloroaurate, ammonium chloroaurate, chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate, platinous chloride, platinum, potassium chloroplatinate, sodium chloroplatinate, diethylamine platinum chloride, platinum nitrate, 1, 5-cyclooctadiene platinum dichloride, potassium trichloro (ethylene) platinate, dichlorotetraammineplatinum, dinitrile phenyl dichloroplatinum, bis (triphenyl phosphite) platinum dichloride, ammonium tetrachloroplatinate, ammonium chloropalladate, sodium chloropalladate, potassium chloropalladate, ammonium chlororhodate, potassium chlororhodate, chloroiridic acid, sodium chloroiridate, potassium chloroiridate and ammonium chloroiridate.
10. A method of preparing a reduced noble metal lone atom material stable in solution according to claim 7, wherein: the reducing agent comprises one or a mixture of more than two of alcohol compounds, glucose, formic acid, citric acid, tartaric acid, ascorbic acid, hydrazine hydrate or borohydride.
11. A method of preparing a reduced noble metal alone atom material stable in solution as claimed in claim 10, wherein: the alcohol compound reducing agent comprises one or a mixture of more than two of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, ethylene glycol and glycerol.
12. A method of preparing a reduced noble metal lone atom material stable in solution according to claim 7, wherein: the temperature range of the reaction is from room temperature to 200 ℃.
13. A method of preparing a reduced noble metal lone atom material stable in solution according to claim 7, wherein: the reaction time ranges from 0.5h to 600 h.
14. A method of preparing a reduced noble metal lone atom material stable in solution according to claim 7, wherein: the quantity ratio change range of the reducing agent and the high oxidation state noble metal precursor is as follows: 1-10 7 。
15. A method of preparing a reduced noble metal lone atom material stable in solution according to claim 7, wherein: the temperature range of the reaction is 50 ℃ to 100 ℃; the reaction time range is 4h to 50 h; the quantity ratio change range of the reducing agent and the high oxidation state noble metal precursor is as follows: 10 2 -10 6 。
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