WO2019079917A1

WO2019079917A1 - Method for preparing precious metal isolated atoms in solution and application

Info

Publication number: WO2019079917A1
Application number: PCT/CN2017/000677
Authority: WO
Inventors: 张宗超; 刘凯瑞; 申星
Original assignee: 中国科学院大连化学物理研究所
Priority date: 2017-10-27
Filing date: 2017-11-13
Publication date: 2019-05-02
Also published as: CN109719304B; CN109719304A

Abstract

A method for preparing precious metal isolated atoms in a solution, comprising mixing a macrocyclic polyether, a precious metal compound precursor in a high oxidation state, a reducing agent, and water; and reducing a precious metal compound in the high oxidation state to precious metal isolated atoms by means of the reducing agent in the solution, so as to obtain a precious metal isolated atom solution. An application in preparation of precious metal isolated atoms in a solution, wherein precious metal isolated atoms are loaded on a solid dielectric to form a precious metal isolated atom-solid dielectric material.

Description

Method and application for preparing noble metal atom in solution

Technical field

The invention belongs to the technical field of invention, and in particular relates to a method and an application for preparing a noble metal atom in a solution.

Background technique

Precious metals are widely used materials in modern industry and scientific research. Precious metals and their alloys have excellent electrical and thermal conductivity, oxidation resistance, corrosion resistance and special magnetic and mechanical properties. They are widely used in aviation, marine, biomedical, iron and steel smelting, petrochemical and electronic equipment. For example, Pt-Ir and Pt-Ni alloys are commonly used spark plug materials; Pt-Pd-Rh three-way catalysts are the main materials for treating automobile exhaust.

The high price of precious metals and the backwardness of manufacturing technology have severely restricted their full use in various fields. For example, in the Pt/Al ₂ O ₃ catalyst of the petroleum catalytic reforming unit, Pt exists in the form of nanoparticles, and thus most of the Pt atoms are contained inside, and cannot be sufficiently contacted with the reaction raw material to catalyze the reaction, resulting in a huge Waste and substantial increase in production costs.

Precious metal orphan atoms and atomic-grade mixed precious metal alloy materials provide ample space for the full utilization of precious metals. However, it is very difficult to synthesize noble metal atoms in solution. Because zero-valent precious metal atoms are not charged, there is no electrostatic repulsion between them, and the degree of freedom of movement in solution is much larger than that of solid surface, so zero-valent noble metal orphan atoms in solution will rapidly aggregate to form clusters or nanoparticles. Therefore, the controlled synthesis of noble metal atoms in solution has always been a huge challenge in the field of science and technology.

Summary of the invention

It is an object of the present invention to provide a method and application for preparing noble metal atoms in a solution. In order to achieve the above object, the technical solution adopted by the present invention is as follows:

A method for preparing a noble metal atom in a solution: a precursor of a noble metal compound containing a macrocyclic polyether, a high oxidation state, and a reducing agent and water are thoroughly mixed. Reductant will be a noble metal compound in a high oxidation state The precursor is reduced to a noble metal atom, thereby obtaining a noble metal atom capable of being stably present in the solution.

The noble metal atom in the method is one of platinum, palladium, rhodium, ruthenium, osmium, iridium, gold, and silver.

The noble metal orphan atoms are preferably platinum and gold.

The platinum orphan atom is mainly characterized by a ¹⁹⁵ Pt nuclear magnetic resonance chemical shift between -2000 and 4000 ppm.

The noble metal compound precursor of the high oxidation state is a platinum compound precursor of a high oxidation state, a palladium compound precursor of a high oxidation state, a ruthenium compound precursor of a high oxidation state, a ruthenium compound precursor of a high oxidation state, a high oxidation state A ruthenium compound precursor, a high oxidation state ruthenium compound precursor, a high oxidation state silver compound precursor or a high oxidation state gold compound precursor.

The platinum compound precursor of the high oxidation state used in the method is: chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate, platinum chloride, platinum chloride, platinum chloride, platinum nitrate, 1 , 5-cyclooctadiene platinum dichloride, trichloro(ethylene)platinic acid, potassium tetraammine platinum, dinitrile phenyl dichloroplatinum, di(triphenyl phosphite) dichloride One of platinum or ammonium tetrachloroplatinate.

The high oxidation state palladium compound precursor used in the method includes: palladium chloride, palladium nitrate, chloropalladium acid, tetraammine palladium dichloride, diammine palladium dichloride, dinitrotetraammine Palladium, palladium acetate, palladium sulfate, palladium trifluoroacetate, palladium acetylacetonate, potassium hexachloropalladate, ammonium hexachloropalladate, tetraammine palladium (II) acetic acid, sodium tetrachloropalladium (II), tetrachloropalladium (II) potassium acid, ammonium tetrachloropalladate, potassium tetracyano palladium (II) acid, potassium tetrabromo palladium (II) acid, palladium pivalate, palladium (II) cyanide, palladium (II) bromide, Palladium (II) thiosulfate, palladium (II) iodide, palladium (II) sulfonate, 1,3-bis(diphenylphosphino)propane) palladium(II) chloride, (1,5-cyclooctane Alkenyl palladium (II), (2,2'-bipyridyl) palladium (II) dichloride, [1,2-bis(diphenylphosphino)ethane]palladium (II) dichloride, One of 1,4-bis(diphenylphosphino)butane-palladium (II) chloride or palladium chloride.

The high oxidation state ruthenium compound precursor used in the method includes: cerium (III) nitrate, cerium (III) acetylacetonate, di(ethylene) chloranil dimer, sodium hexachloro ruthenium (III), and six Potassium chlorate (III) acid, ammonium hexachloroantimonate, Cerium (III) chloride, tris(triphenylphosphine)phosphonium chloride (I), tris(ethylenediamine) antimony trichloride, acetylacetonyl bis(ethylene)phosphonium (I), dicarbonylacetyl One of acetone oxime (I), dicarbonyl pentamethylcyclopentadienyl quinone or bis(1,5-cyclooctadiene) ruthenium tetrafluoroborate (I).

The high oxidation state ruthenium compound precursor used in the method includes: chlorodecanoic acid, ruthenium (III) acetylacetonate, sodium hexachlorostilbene (III), potassium hexachloroantimonate (III), hexachloroantimonic acid Ammonium, potassium hexanitroguanidate (III), barium (III) chloride, barium (III) bromide, 1,5-cyclooctadiene (acetylacetonate) ruthenium (I), 1,5-cyclooctane Ethene (hexafluoroacetylacetone) ruthenium (I), pentamine ruthenium chloride (III), dichlorotetrakis(2-(2-pyridyl)phenyl)diruthenium (III), dicarbonyl acetylacetone Bismuth (I), bis(1,5-cyclooctadiene) ruthenium (I) tetrafluoroborate, 1,5-cyclooctadiene (pyridine) (tricyclohexylphosphine) ruthenium hexafluorophosphate or double One of [1,2-bis(diphenylphosphino)ethane]carbonylchloroindole (I).

The high oxidation state ruthenium compound precursor used in the method includes: antimony trichloride, ruthenium (III) acetylacetonate, bismuth nitrite (III) solution, hexaammine ruthenium chloride, ammonium hexachloroantimonate, Potassium hexacyanophthalate (II), ammonium tetrapropyl perrhenate, cerium (III) chloride, ruthenium pentoxide (III) hydrate, cerium (III) iodide hydrate, three ( Triphenylphosphine) ruthenium (II) dichloride, hexaammonium trichloride ruthenium, triphenylphosphine ruthenium chloride, dichloro (2,6,10-dodecatriene-1,12-diyl ) cerium (IV), dichlorotris(1,10-phenanthroline) ruthenium (II), dichlorodicarbonylbis(triphenylphosphine)ruthenium(II) or pentamine chloride ruthenium chloride (III) One of them.

The high oxidation state ruthenium compound precursor used in the method includes potassium citrate dihydrate, potassium hexachloroantimonate (IV), ammonium hexachloroammonium, bis(pentamethylcyclopentadienyl) ruthenium (II). And one of cerium (III) chloride or pentaammine (trifluoromethanesulfonate) ruthenium (III) trifluoromethanesulfonic acid.

The high-oxidation gold compound precursor used in the method comprises: potassium chloroaurate, sodium cyanide (I), gold monochloride, gold trioxide, trichloro(pyridine) gold (III), three Gold chloride, sodium tetrachloroaurate (III), tetrachloroauric acid, ammonium tetrachloroaurate, chlorine (dimethyl sulfide) gold (I), chlorocarbonyl fund (I), gold cyanide, bromination Gold, iodized gold or one of triphenylphosphonium chloride (I).

The high oxidation state silver compound precursor used in the method includes: silver nitrate, silver lactate, and lemon Silver citrate, silver chlorate, silver cyanate, silver bromate, silver acetate, silver trifluoroacetate, silver acetylacetonate, potassium dicyanate, silver pentafluoropropionate, silver cyanide or silver benzoate One.

The alcohol reducing agent used in the method comprises: methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, ethylene glycol or glycerol.

The non-alcohol reducing agent used in the method comprises: glucose, formic acid, citric acid, tartaric acid, ascorbic acid, hydrazine hydrate, borohydride.

The macrocyclic polyether is:

Wherein: n=1-10000; m=1-10000; p=1-10000; q=1-10000; r=1-10000; R, R'=S, N, P, As; R”=

Macrocyclic polyether crown ether

n=1-10000,

The macrocyclic polyether crown ether is preferred

n=1-3.

The ratio of the amount of the reducing agent to the amount of the noble metal compound precursor in the high oxidation state is not lower than the stoichiometric ratio required to reduce the noble metal compound precursor of the high oxidation state.

The ratio of the amount of the reducing agent to the amount of water is not less than 10 ^{-4 :} 1.

The ratio of the amount of the substance between the macrocyclic polyether substance and the high oxidation state noble metal compound precursor is not less than 1:1.

The temperature range is from -50 ° C to 200 ° C, and the reaction time is from 0.5 to 168 h.

The application of a noble metal atom is carried out by depositing a noble metal atom in a solution on a solid medium to form a noble metal atom-solid medium new material, and the preparation process adopts a dipping method, including the following steps:

1) impregnation: the carrier is thoroughly mixed with the noble metal atomic solution protected by the macrocyclic polyether, and immersed at room temperature for 0.5-24 hours;

2) Removal of reducing agent and water: vacuum decompression treatment to remove reducing agent and water.

3) Heat treatment: vacuum drying at 20-200 ° C for 0.5-48 hours.

The loading amount of the noble metal orphan atom: 0.01-20%.

The invention adopts the macrocyclic polyether as a protective agent, realizes the controllable synthesis of the noble metal atom in the solution, and carries the precious metal orphan atom in the solution on the surface of the solid medium to form a precious metal isolated atom-solid medium new material.

The invention realizes the preparation of the isolated noble metal atom in the solution phase. Compared with the synthesis of the metal material in the conventional solution phase, the formation of the metal nanoparticles is avoided, and the reduced atomic solution is obtained. Compared with solid surface supported monoatomic materials, it has high load capacity and good stability.

DRAWINGS

Figure 1 is an ultraviolet visible spectrum of Examples 1, 4, 5, 6, and 7.

2 is an ultraviolet visible spectrum of Example 2.

Figure 3 is an ultraviolet visible spectrum of Example 3.

4 is an ultraviolet visible spectrum of Example 8.

Figure 5 is an infrared spectrum of the adsorption of CO of Examples 9, 10, 11 on a 1 wt% platinum ion-alumina new material.

Detailed ways

The invention will be further described in detail below by taking the synthesis of platinum orphan atoms and gold orphan atoms as an example. The protection of the patent is not limited to the specific embodiments, but is limited by the claims.

Example 1

Preparation of platinum atom in solution: 0.1946g 15-crown ether-5,135ml ethanol, 10.2ml water and 4.8ml concentration of 0.018404mol/L chloroplatinic acid solution are mixed thoroughly, then warmed up, condensed and refluxed at 80 °C 6 The chloroplatinic acid is completely reduced in an hour. The UV-visible absorption spectrum (Fig. 1) shows that chloroplatinic acid is completely reduced. (Note: The UV absorption peak at 264.5 nm represents the absorption peak of PtCl ₆ ^2- ion, and the disappearance of the UV absorption peak indicates that chloroplatinic acid is completely reduced.)

Example 2

Preparation of platinum solitary atoms in solution: 0.1946 g of 15-crown ether-5,135 ml of ethanol, 10.2 ml of water and 4.8 ml of a concentration of 0.018404 mol/L chloroplatinic acid solution are thoroughly mixed, and then the temperature is raised, and the mixture is refluxed at 200 ° C for 0.5. The chloroplatinic acid is completely reduced in an hour. The UV-visible map is shown in Figure 2, indicating that chloroplatinic acid is completely reduced. Explanation: The ultraviolet absorption peak at 264.5 nm represents the absorption peak of PtCl ₆ ^2- ion, and the disappearance of the ultraviolet absorption peak indicates that chloroplatinic acid is completely reduced. .

Example 3

Preparation of platinum atom in solution: 0.1946g 15-crown ether-5,135ml ethanol, 10.2ml water and 4.8ml concentration of 0.018404mol/L chloroplatinic acid solution are mixed thoroughly, then warmed up at 25 ° C (room temperature) The chloroplatinic acid was completely reduced by reduction for 168 hours (one week). The UV-visible map is shown in Figure 3, indicating that chloroplatinic acid is completely reduced. Explanation: The ultraviolet absorption peak at 264.5 nm represents the absorption peak of PtCl ₆ ^2- ion, and the disappearance of the ultraviolet absorption peak indicates that chloroplatinic acid is completely reduced.

Example 4

Preparation of platinum solitary atoms in solution: 0.0195 g of 15-crown ether-5 (a ratio of crown ether to platinum is 1:1), 135 ml of ethanol, 10.2 ml of water and 4.8 ml of a concentration of 0.018404 mol/L chloroplatinum The acid solution was thoroughly mixed, then heated, and condensed and refluxed at 80 ° C for 6 hours to completely reduce chloroplatinic acid. The UV-visible spectrum is shown in Figure 1, indicating that chloroplatinic acid is completely reduced. Explanation: The ultraviolet absorption peak at 264.5 nm represents the absorption peak of PtCl ₆ ^2- ion, and the disappearance of the ultraviolet absorption peak indicates that chloroplatinic acid is completely reduced.

Example 5

Preparation of platinum solitary atoms in solution: 0.1946g of 15-crown ether-5, 40.5mg of ethanol (the ratio of the amount of ethanol to chloroplatinic acid is 10:1) ethanol, 150ml of water (the ratio of the amount of ethanol to water) 1 : 10000) and 4.8 ml of a concentration of 0.018404 mol / L chloroplatinic acid solution were thoroughly mixed, and then the temperature was raised, and condensed and refluxed at 80 ° C for 6 hours to completely reduce chloroplatinic acid. The UV-visible spectrum is shown in Figure 1, indicating that chloroplatinic acid is completely reduced. Explanation: The ultraviolet absorption peak at 264.5 nm represents the absorption peak of PtCl ₆ ^2- ion, and the disappearance of the ultraviolet absorption peak indicates that chloroplatinic acid is completely reduced.

Example 6

Preparation of platinum atom in solution: 0.1946g 15-crown ether-5,882g ethanol (1.14L, ethanol is added in an amount of 10 ⁷ times the amount of chloroplatinic acid), 10.2ml water and 4.8ml concentration is 0.018404mol The /L chloroplatinic acid solution was thoroughly mixed, then heated, and condensed and refluxed at 80 ° C for 6 hours to completely reduce chloroplatinic acid. The UV-visible spectrum is shown in Figure 1, indicating that chloroplatinic acid is completely reduced. Note: The ultraviolet absorption peak at 264.5 nm represents the absorption peak of PtCl ₆ ^2- ion, and the disappearance of the ultraviolet absorption peak indicates that chloroplatinic acid is completely reduced.

Example 7

Preparation of platinum solitary atoms in solution: 0.1946 g of 15-crown ether-5, 148.5 ml of ethanol, 1.5 ml of water (the ratio of the amount of ethanol to water is 30:1) and 4.8 ml of the concentration of 0.018404 mol/L chloroplatinum The acid solution was thoroughly mixed, then heated, and condensed and refluxed at 80 ° C for 6 hours to completely reduce chloroplatinic acid. The UV-visible spectrum is shown in Figure 1, indicating that chloroplatinic acid is completely reduced. Explanation: The ultraviolet absorption peak at 264.5 nm represents the absorption peak of PtCl ₆ ^2- ion, and the disappearance of the ultraviolet absorption peak indicates that chloroplatinic acid is completely reduced.

Example 8

Preparation of gold solitary atoms in solution: 0.2335 g of 18-crown-6, 135 ml of ethanol, 11.4 ml of water and 3.6 ml of a solution of 0.02428 mol/L of chloroauric acid are thoroughly mixed, then heated, and condensed and refluxed at 80 ° C for 27 hours. The chloroauric acid is completely reduced. The UV-visible absorption spectrum (Fig. 4) shows that chloroauric acid is completely reduced. (Note: The ultraviolet absorption peak at 320.6 nm represents the absorption peak of AuCl4- ions, and the disappearance of the ultraviolet absorption peak indicates that chloroauric acid is completely reduced.)

Example 9

A platinum atom-alumina new material was prepared by impregnating platinum atoms in a solution by impregnation. 87 ml of a platinum atomic solution obtained in Example 1 was added, and 1 g of γ-Al ₂ O _{3 was added} and fully immersed for 1 hour. Ethanol and water were distilled off under reduced pressure at 40 ° C, and dried under vacuum at 40 ° C for 12 hours to obtain a platinum atom-aluminum oxide new material having a loading of 1%. The infrared spectrum of CO adsorption on 1 wt% platinum ion-alumina (Fig. 5) shows that the platinum atom-alumina new material was successfully synthesized. (Note: The peak between 1800 cm ^{-1 and} 1900 cm ^-1 is attributed to the bridge adsorption peak of CO on platinum, and the peak at 2080 cm ^-1 is the linear adsorption peak of CO on platinum. It can be seen from the figure There is no bridge adsorption peak, which means that there are no two or more platinum atoms connected. As the CO pressure increases, the peak position at 2080 cm ^-1 does not shift blue, which indicates that platinum is isolated. The existence of the atomic form proves the successful synthesis of the platinum atom-aluminum new material.

Example 10

A platinum atom-alumina new material was prepared by impregnating platinum atoms in a solution by impregnation. 87 ml of a platinum atomic solution obtained in Example 1 was added, 100 g of γ-Al ₂ O _{3 was added,} and fully immersed for 1 hour. Ethanol and water were distilled off under reduced pressure at 40 ° C, and vacuum-dried at 150 ° C for 0.5 hour to obtain a platinum atom-alumina new material having a loading of 0.01%. The infrared spectrum of CO adsorption on 1 wt% platinum ion-alumina is shown in Fig. 5.

Example 11

A platinum atom-alumina new material was prepared by impregnating platinum atoms in a solution by impregnation. 87 ml of a platinum atomic solution obtained in Example 1 was added, 0.1 g of γ-Al ₂ O _{3 was added,} and fully immersed for 1 hour. Ethanol and water were distilled off under reduced pressure at 40 ° C, and dried under vacuum at 20 ° C for 48 hours to obtain a platinum atom-aluminum oxide new material having a loading of 10%. The infrared spectrum of CO adsorption on 1 wt% platinum ion-alumina is shown in Fig. 5.

Claims

A method for preparing a noble metal atom in a solution, characterized in that a macrocyclic polyether, a noble metal compound precursor of a high oxidation state, a reducing agent and water are thoroughly mixed according to a certain ratio, and a reducing agent in the solution is a noble metal in a high oxidation state. The compound precursor is reduced to a zero-valent noble metal orphan atom, thereby obtaining a noble metal orphan atom solution which can be stably present.
The method for preparing a noble metal atom in a solution according to claim 1, wherein the noble metal atom is a platinum element or a post platinum element; and the platinum element is palladium, rhodium, ruthenium or iridium. , ruthenium or platinum; the post-platinum element is silver or gold.
A method of preparing a noble metal atom in a solution according to claim 1, wherein said noble metal atom is preferably platinum and gold.
A method for preparing a noble metal atom in a solution according to claim 3, wherein said platinum atom is characterized by a 195 Pt nuclear magnetic resonance chemical shift between -2000 and -4000 ppm.
The method for preparing a noble metal atom in a solution according to claim 1, wherein the precursor of the noble metal compound in the high oxidation state is a platinum compound precursor of a high oxidation state, a palladium compound precursor of a high oxidation state, High oxidation state ruthenium compound precursor, high oxidation ruthenium compound precursor, high oxidation ruthenium compound precursor, high oxidation ruthenium compound precursor, high oxidation state silver compound precursor or high oxidation state gold Compound precursor.
The method for preparing a noble metal atom in a solution according to claim 1, wherein the noble metal platinum compound precursor of the high oxidation state comprises: chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate, chlorination Platinum, platinum chloride, platinum chloride, platinum nitrate, 1,5-cyclooctadiene platinum dichloride, trichloro-(ethylene) potassium platinum phosphate, platinum tetraammine platinum, dinitrile One of phenyl dichloroplatinum, bis(triphenyl phosphite) platinum dichloride or ammonium tetrachloroplatinate.
A method for preparing a noble metal atom in a solution according to claim 1, characterized in that The noble metal palladium compound precursor in the high oxidation state includes: palladium chloride, palladium nitrate, chloropalladium acid, tetraammine palladium dichloride, diammine palladium dichloride, dinitrotetraammine palladium, Palladium acetate, palladium sulfate, palladium trifluoroacetate, palladium acetylacetonate, potassium hexachloropalladate, ammonium hexachloropalladate, tetraammine palladium (II) acetic acid, sodium tetrachloropalladium (II), tetrachloropalladium (II) Acid potassium, ammonium tetrachloropalladate, potassium tetracyano palladium (II) acid, potassium tetrabromo palladium (II) acid, palladium pivalate, palladium (II) cyanide, palladium (II) bromide, thio Palladium (II) sulfate, palladium (II) iodide, palladium (II) sulfonate, 1,3-bis(diphenylphosphino)propane) palladium (II) chloride, (1,5-cyclooctadiene) Palladium (II) dichloride, (2,2'-bipyridyl) palladium (II) dichloride, [1,2-bis(diphenylphosphino)ethane]palladium(II) dichloride, 1, One of 4-bis(diphenylphosphino)butane-palladium (II) chloride or palladium chloride.
The method for preparing a noble metal atom in a solution according to claim 1, wherein the noble metal ruthenium compound precursor in the high oxidation state comprises: cerium (III) nitrate, cerium (III) acetylacetonate, and bis(ethylene) Chloroquinone dimer, sodium hexachloroantimonate (III), potassium hexachloroantimonate (III), ammonium hexachloroantimonate, cerium (III) chloride, cerium tris(triphenylphosphine) I), tris(ethylenediamine) antimony trichloride, acetylacetonyl bis(ethylene) ruthenium (I), dicarbonyl acetylacetonate oxime (I), dicarbonyl pentamethylcyclopentadienyl or double (1,5-cyclooctadiene) one of cerium (I) tetrafluoroborate.
A method for preparing a noble metal atom in a solution according to claim 1, wherein the noble metal ruthenium compound precursor in the high oxidation state comprises: chloroantimonic acid, ruthenium (III) acetylacetonate, and hexachloropyrene ( III) sodium, potassium hexachloroantimonate (III), ammonium hexachloroantimonate, potassium hexanitroguanidate (III), cerium (III) chloride, cerium (III) bromide, 1,5-cyclooctane Diene (acetylacetone) ruthenium (I), 1,5-cyclooctadiene (hexafluoroacetylacetonate) ruthenium (I), pentamine ruthenium chloride (III), dichlorotetrakis (2-( 2-pyridyl)phenyl)diguanium(III), bis(1,5-cyclooctadiene) ruthenium (I) tetrafluoroborate, 1,5-cyclooctadiene (pyridine) (tricyclohexylphosphine) cesium hexafluorophosphate or one of bis[1,2-bis(diphenylphosphino)ethane]carbonyl chloroguanidine (I).
The method for preparing a noble metal atom in a solution according to claim 1, wherein the noble metal ruthenium compound precursor in the high oxidation state comprises: antimony trichloride, cerium (III) acetylacetonate, and sub Niobium (III) nitrate solution, hexaammine ruthenium chloride, ammonium hexachloroantimonate, potassium hexacyanophthalate (II), ammonium tetrapropyl perrhenate, ruthenium (III) chloride Hydrated pentachlorophosphonium (III) hydride, cerium (III) iodide hydrate, tris(triphenylphosphine) ruthenium dichloride (II), hexaammonium trichloride ruthenium, triphenylphosphine ruthenium chloride, Dichloro(2,6,10-dodecatriene-1,12-diyl)ruthenium (IV), dichlorotris(1,10-phenanthroline)ruthenium (II), dichlorodicarbonyl bis ( Triphenylphosphine) ruthenium (II) or pentylene chloride dichloropyridinium (III).
The method for preparing a noble metal atom in a solution according to claim 1, wherein the noble metal ruthenium compound precursor in the high oxidation state comprises: potassium citrate dihydrate, potassium hexachloroantimonate (IV), One of hexachloroammonium, bis(pentamethylcyclopentadienyl)ruthenium (II), ruthenium (III) chloride or pentaamine (trifluoromethanesulfonate) ruthenium (III) trifluoromethanesulfonic acid .
A method for preparing a noble metal atom in a solution according to claim 1, wherein said noble metal gold compound precursor in a high oxidation state comprises: potassium chloroaurate, sodium cyanide (I), monochlorination Gold, gold trioxide, trichloro(pyridine) gold (III), gold trichloride, sodium tetrachlorogold (III), tetrachloroauric acid, ammonium tetrachloroaurate, chlorine (dimethyl sulfide) gold (I), one of chlorocarbonyl fund (I), gold cyanide, gold bromide, gold iodide or triphenylphosphine chloride (I).
The method for preparing a noble metal atom in a solution according to claim 1, wherein the noble metal silver compound precursor of the high oxidation state comprises: silver nitrate, silver lactate, silver citrate, silver chlorate, cyanic acid Silver, silver bromate, silver acetate, silver trifluoroacetate, silver acetylacetonate, potassium dicyanate, silver pentafluoropropionate, silver cyanide or silver benzoate.
The method for preparing a noble metal atom in a solution according to claim 1, wherein the reducing agent is one of an alcohol compound, glucose, formic acid, citric acid, tartaric acid, ascorbic acid, hydrazine hydrate, and borohydride. Kind or several.
A method for preparing a noble metal atom in a solution according to claim 1, wherein the reducing agent is methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol, ortho Ding One or a mixture of alcohols, ethylene glycol or glycerol.
A method of preparing a noble metal atom in a solution according to claim 1, wherein said macrocyclic polyether is:

Wherein: n=1-10000; m=1-10000; p=1-10000; q=1-10000; r=1-10000; R, R'=S, N, P, As;
A method for preparing a noble metal atom in a solution according to claim 1, characterized in that said macrocyclic polyether crown ether
n=1-10000, preferred
n=1-3.
A method for preparing a noble metal atom in a solution according to claim 1, wherein the ratio of the amount of the reducing agent to the noble metal compound precursor in the high oxidation state is not lower than the noble metal in the reduced high oxidation state. The stoichiometric ratio required for the compound precursor.
A method of preparing a noble metal atom in a solution according to claim 1, wherein the ratio of the amount of the reducing agent to water is not less than 10 -4 : 1.
A method of preparing a noble metal atom in a solution according to claim 1, wherein the ratio of the amount of the substance between the macrocyclic polyether substance and the high oxidation state noble metal compound precursor is not less than 1:1.
The use of a noble metal atom in a solution is characterized in that a noble metal atom is carried on a solid medium to form a noble metal atom-solid medium new material.