WO2020155672A1 - 一种在溶液中稳定的还原态贵金属孤原子材料和制备方法 - Google Patents

一种在溶液中稳定的还原态贵金属孤原子材料和制备方法 Download PDF

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WO2020155672A1
WO2020155672A1 PCT/CN2019/111843 CN2019111843W WO2020155672A1 WO 2020155672 A1 WO2020155672 A1 WO 2020155672A1 CN 2019111843 W CN2019111843 W CN 2019111843W WO 2020155672 A1 WO2020155672 A1 WO 2020155672A1
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noble metal
atom
platinum
lone
solution according
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张宗超
李会香
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中国科学院大连化学物理研究所
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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
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0545—Dispersions or suspensions of nanosized particles
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention belongs to the field of new material invention, and the specific material is a reduced precious metal lone atom material that is stable in a protective agent-containing solution.
  • precious metals and their alloys have become widely used materials in modern industries due to their excellent properties. Due to its high temperature corrosion resistance, high reliability, high precision and long service life, precious metals are widely used in the manufacture of precision instruments for aerospace, marine industry and military industry, such as springs, bellows, conductive hairsprings, and shafts. Tips and other originals. At the same time, due to its material's physiological non-toxicity, good ductility and biocompatibility, precious metals are widely used in the preparation of medical materials. For example, in the dental field, two major dental precious metal alloys, amalgam alloys and casting alloys, medical gold needles, silver needles and hard needles, and electrode materials for medical electronic equipment.
  • precious metals have unique catalytic performance and stability, especially platinum group metals (iridium, rhodium, palladium and platinum), which are widely used in petrochemicals, hydrogen fuel cells and other fields.
  • platinum group metals iridium, rhodium, palladium and platinum
  • the scarcity of precious metal resources and the backward manufacturing technology make the price of precious metals high, which severely restricts their full utilization in various fields.
  • the precious metal solitary atoms provide a broad space for the utilization of precious metals.
  • Maria Flytzani-Stephanopoulos et al. (Acc. Chem. Res, 2014, 47, 783.) reported the synthesis of Au monoatomic materials on various carriers and successfully applied them to water gas shift reactions.
  • Tao Zhang et al. (Nature Chem., 2011, 3,634.) reported the synthesis of Pt monoatomic materials on the surface of iron oxide and successfully applied it to the oxidation reaction of carbon monoxide, which increased the conversion frequency of the reaction by 2-3 times.
  • the monoatomic materials obtained by the method of solid surface dispersion not only have many problems such as low loading, instability, etc., at the same time, due to the interaction between the solid surface and the precious metal monoatoms, the precious metal monoatoms do not exist in an isolated state.
  • the existence state is bound to the solid surface and has a strong interaction with the oxygen on the carrier.
  • the metal center is not in a completely reduced state (Nature Nanotechnology, 2018, 13,856; Nature Commu., 2019, 10,234), and it is not easy to peel off from the solid surface. Therefore, it cannot be used as a raw material to generate and prepare a wider range of substances.
  • the reduced noble metal atoms have a large degree of freedom in the movement of the solution, and it is easy to aggregate to cause the generation of nanoparticles. Therefore, it has always been a huge challenge in the field of science and technology to disperse the reduced noble metal atoms in a solution to obtain isolated noble metal atoms.
  • Vinylpyrrolidone polymer and isopropylacrylamide polymer etc. J. Phys. Chem. B, 1999, 103, 3818.; Langmuir 1997, 13, 6465.
  • High-molecular polymers are widely used in the synthesis of precious metal materials in solution. However, these high-molecular polymers are difficult to prevent the solitary precious metal atoms in the initial reduced state from gathering and growing into nanoparticles.
  • Surfactants are also used in the synthesis of precious metal materials in solution, but they are difficult to remove, and the freedom of precious metal lone atoms wrapped by surfactants is limited (Patent No.: 201611004958.3), and the polymer remaining in the material Polymers and surfactants also affect the application characteristics of the material.
  • the invention introduces a stable reduced noble metal lone atom material in solution and a preparation method, which can stably exist in a solvent containing a protective group. This is different from the metal organic compounds reported in the literature.
  • Marc-Etienne Moret, Bele'n Gil, etc. introduced various types of metal complexes (Higher oxidation state organopalladium 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.
  • Pt and Ag metal bonds exist in the form of ions, namely Pt(II), Ag(I), and there are containing Phosphorus, carbon and other ligands.
  • Metal Pd atom complex And the structure is In the complex, there are nitrogen and carbon ligands around the metal center to stabilize the structure.
  • the valence state of the metal is a non-reduced state, and the metal center in its structure forms a metal-carbon bond, a metal-nitrogen or a metal-phosphorus bond with a nitrogen-containing, phosphorous, or carbon-containing ligand. That is, the reported metal complexes are metal organic compounds. This is different from a metal lone atom material that is stable in solution introduced in the invention.
  • the reduced noble metal lone atom material that is stable in solution in the present invention can be used in the fields of material preparation, industrial catalysis and the like.
  • the reduced Pt solitary material can be used in the hydrosilylation reaction of unsaturated compounds (the hydrosilylation reaction refers to the addition reaction of the compound containing the Si-H bond and the unsaturated organic compound to form an organic silicon compound One type of reaction).
  • the reduced Au solitary material can be used in low temperature conditions such as carbon monoxide oxidation reaction.
  • the reduced precious metal lone atom material can also be used in material coating.
  • the purpose of the present invention is to provide a reduced precious metal lone atom material that is stable in solution.
  • the material is composed of reduced precious metal solitary atoms and a protective agent.
  • the protective agent includes but is not limited to chain ether compounds.
  • the noble metal lone atom mentioned in the invention refers to an independent existence, no metal bond is formed between metals, and the chemical valence of the noble metal is not higher than the positive univalent, which is 0, or a mixture of 0 and positive univalent, preferably 0 price.
  • the proportion of the metal lone atom in the solution with zero valence is at least 30%.
  • the proportion of the chemical state of the metal lone atom in the solution is not less than 80%.
  • the noble metal lone atom is a platinum atom or a gold atom.
  • the protective agent includes but is not limited to one or two or more of compounds with ether structure; the protective agent includes but is not limited to one or two or more of compounds with glycol ether structure; includes but It is not limited to one or two or more compounds of glycol ethers and propylene glycol ether structures.
  • the protective agent includes but is not limited to ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether One or more of ether, triethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol diethyl ether, and n-butyl ether.
  • the molar ratio of the noble metal lone atom to the protective agent is less than or equal to 1:1, and the preferred range is 10 to 10 6 .
  • the concentration range of the noble metal lone atoms is greater than 0 to 1 mol/L.
  • the concentration of the noble metal lone atoms ranges from 0.01 to 50 mmol/L.
  • the composition of the material in the preparation process includes but is not limited to chain ether compounds, high oxidation state precious metal compound precursors, reducing agents, or includes but not limited to chain ether compounds, high oxidation state precious metal compound precursors, reduction Reagent, water; all components are fully mixed according to the required ratio into a liquid system, and a stable precious metal monoatomic solution can be obtained after the reaction.
  • the material preparation process can include one or two or three of the following three situations to make the mixed system liquid;
  • the first type water can be included in the composition, the mass concentration range of water is 0-70%, and water can be used as a solvent composition;
  • the second type when the chain ether compound in the composition contains a protective agent that is liquid at room temperature, the liquid chain ether compound can be used as a solvent composition;
  • the third type when the reducing agent in the composition contains a reducing agent that is liquid at room temperature, the liquid reducing agent can be used as a solvent composition.
  • the high oxidation state noble metal compound precursors include, but are not limited to, high oxidation state platinum compound precursors (one or two of positive divalent and positive tetravalent), high oxidation state palladium compound precursors (positive divalent, positive four One or two of the valence), high oxidation state rhodium compound precursor (positive trivalent), high oxidation state iridium compound precursor (one or two of positive trivalent and positive tetravalent), high oxidation state Ruthenium compound precursor (positive trivalent), high oxidation state osmium compound precursor (positive divalent, positive trivalent, positive tetravalent one or two or three) or high oxidation state gold compound precursor (positive trivalent) One or more of them.
  • the high oxidation state noble metal compound precursors include but are not limited to: chloroauric acid, sodium chloroauric acid, potassium chloroauric acid, ammonium chloroauric acid, chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate, and chlorinated Platinum, platinum chloride, potassium chloroplatinate, sodium chloroplatinate, diethylamine platinum chloride, platinum nitrate, 1,5-cyclooctadiene platinum dichloride, trichloro(ethylene) platinum acid Potassium, dichlorotetraammine platinum, dinitrile phenyl dichloroplatinum, bis(triphenyl phosphite) platinum dichloride, ammonium tetrachloroplatinate, ammonium chloropalladate, sodium chloropalladate, chloropalladic acid
  • the reducing agent includes but is not limited to one or a mixture of alcohol compounds, glucose, formic acid, citric acid, tartaric acid, ascorbic acid, hydrazine hydrate, or borohydride.
  • the alcohol compound reducing agent includes but is not limited to one of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, ethylene glycol, glycerol, or Two or more mixtures.
  • the present invention provides a material of stable reduced noble metal lone atoms in solution. It is composed of reduced precious metal lone atoms and protective agent.
  • a chain compound containing an ether bond group is used as a protective agent to stabilize the existence of the reduced noble metal lone atom.
  • chain ether compounds are used as protective agents for the first time to prepare precious metal solitary atom materials in solution, which avoids the accumulation of primary solitary atoms in the synthesis process to cause the generation of nanoparticles.
  • the reduced solitary atoms of the material are different from metal nanoparticles, and can be used in the fields of energy materials, pharmaceutical synthesis, medical materials, catalyst preparation and other fields. It also provides a basic lone atom raw material for the synthesis of a controllable number of the same or different metal clusters and nanomaterials.
  • Figure 1 shows the UV-Vis spectra of Examples 1, 8, 9, 10
  • Figure 2 shows the 195PtNMR spectra of Examples 1, 3, 4, 5, 6, 7, 8, 9, 10
  • Figure 3 shows the UV-Vis spectra of Examples 2, 12
  • Figure 4 is the UV-Vis spectrum of Example 3
  • Figure 5 is the UV-Vis spectrum of Example 4.
  • Figure 6 is the UV-Vis spectrum of Example 5
  • Figure 7 is the UV-Vis spectrum of Example 6
  • Figure 8 is the UV-Vis spectrum of Example 7
  • Figure 10 is one of the high-resolution spherical aberration correction scanning transmission electron microscope analysis diagrams of Example 13
  • Fig. 12 is a high-resolution spherical aberration correction scanning transmission electron microscope analysis diagram of Example 14.
  • the ultraviolet absorption peak at 265 nm represents the absorption peak of PtCl62-. Extending, the intensity of the ultraviolet absorption peak gradually weakened to disappear (from top to bottom), indicating that chloroplatinic acid was gradually reduced to complete reduction).
  • the 195Pt NMR spectrum is the same as Figure 2. Analysis after 240h, the result remains unchanged. (Note: The 195Pt NMR of K2PtCl6 is at 0 ppm, the peak of PtCl42- is at -1617 ppm, and the 195Pt NMR peak of Pt solitary atoms is at -2755 ppm.
  • the ultraviolet absorption peak at 265 nm represents the absorption peak of PtCl62-. With time Prolonged, the intensity of the ultraviolet absorption peak gradually weakened to disappear (from top to bottom), indicating that chloroplatinic acid was gradually reduced to complete reduction).
  • the 195Pt NMR spectrum is the same as that shown in Figure 2. (Note: The 195Pt NMR of K2PtCl6 is at 0ppm, the peak of PtCl42- is at -1617ppm, and the 195Pt NMR peak of Pt solitary atoms is at -2755ppm.
  • the ultraviolet absorption peak at 265nm represents the absorption peak of PtCl62-. With time Extending, the intensity of the ultraviolet absorption peak gradually weakened to disappear (from top to bottom), indicating that chloroplatinic acid was gradually reduced to complete reduction).
  • the 195Pt NMR spectrum is the same as that shown in Figure 2. (Note: The 195Pt NMR of K2PtCl6 is at 0ppm, the peak of PtCl42- is at -1617ppm, and the 195Pt NMR peak of Pt solitary atoms is at -2755ppm.
  • the ultraviolet absorption peak at 265 nm represents the absorption peak of PtCl62-. Extending, the intensity of the ultraviolet absorption peak gradually weakened to disappear (from top to bottom), indicating that chloroplatinic acid was gradually reduced to complete reduction).
  • the 195Pt NMR spectrum is the same as that shown in Figure 2. (Note: The 195Pt NMR of K2PtCl6 is at 0ppm, the peak of PtCl42- is at -1617ppm, and the 195Pt NMR peak of Pt solitary atoms is at -2755ppm.
  • the ultraviolet absorption peak at 265 nm represents the absorption peak of PtCl62-. With time Extending, the intensity of the ultraviolet absorption peak gradually weakened to disappear (from top to bottom), indicating that chloroplatinic acid was gradually reduced to complete reduction).
  • the 195Pt NMR spectrum is the same as that shown in Figure 2. (Note: The 195Pt NMR of K2PtCl6 is at 0ppm, the peak of PtCl42- is at -1617ppm, and the 195Pt NMR peak of Pt solitary atoms is at -2755ppm.
  • the UV-Vis spectrum has the same trend as the lines shown in Figure 1, and the spectrum is similar (Note: During the preparation process, use an ultraviolet spectrum analyzer to analyze the changes in the absorption intensity of the PtCl 6 2- ion peak over time. UV at 265 nm The absorption peak represents the absorption peak of PtCl 6 2- . With the extension of time, the intensity of the UV absorption peak gradually weakened to disappear (from top to bottom), indicating that chloroplatinic acid was gradually reduced to complete reduction); its 195 PtNMR spectrum The figure is the same as Figure 2.
  • the UV-Vis spectrum has the same trend as that shown in Figure 1, and the spectrum is similar.
  • an ultraviolet spectrum analyzer to analyze the changes in the absorption intensity of the PtCl 6 2- ion peak over time, as shown in Figure 1. Show.
  • the ultraviolet absorption peak at 265nm represents the absorption peak of PtCl 6 2- .
  • the intensity of the ultraviolet absorption peak gradually weakened to disappear (from top to bottom), indicating that chloroplatinic acid was gradually reduced to complete reduction).
  • the 195 PtNMR spectrum is the same as Figure 2.
  • the value at 265 nm The UV absorption peak represents the absorption peak of PtCl 6 2- . As time goes by, the intensity of the UV absorption peak gradually weakens to disappear (from top to bottom), indicating that chloroplatinic acid is gradually reduced to complete reduction).
  • the 195 PtNMR spectrum is the same as Figure 2. (Note: The 195 Pt NMR of K 2 PtCl 6 is at 0 ppm, the peak of PtCl 4 2- is at -1617 ppm, and the 195 Pt NMR peak of Pt lone atoms is at -2755 ppm. At the same time, no platinum nanoparticles are detected. The extreme shift and wide peak: -35000ppm to 10000ppm, which shows that H 2 PtCl 6 is completely reduced and Pt lone atoms are generated, and no Pt nanoparticles are generated).
  • an ultraviolet spectrum analyzer is used to analyze the changes in the absorption intensity of AuCl 4 - ions over time. As shown in Figure 3, As time goes by, the intensity of the UV absorption peak gradually weakens (from top to bottom), indicating that the chloroauric acid is gradually reduced.)
  • the stainless steel sheet (2cm*3cm) is placed in the gold solitary atom solution prepared above , After 2 hours, a stainless steel sheet with gold-plated surface can be obtained.

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Abstract

一种溶液中稳定的还原态贵金属孤原子的材料，由还原态贵金属孤原子和保护剂组成。以含有醚键基团的链状化合物为保护剂，使还原态贵金属孤原子稳定存在，在溶液中制得贵金属孤原子材料，避免了合成过程中初级孤原子的聚积导致纳米粒子的产生。该材料的还原态孤原子区别于金属纳米粒子，可用于能源材料、医药合成、医疗材料、催化剂制备等领域。为数目可控的同种或异种金属团簇、纳米材料的合成提供了基础孤原子原料。还涉及一种溶液中稳定的还原态贵金属孤原子材料的制备方法。

Description

一种在溶液中稳定的还原态贵金属孤原子材料和制备方法 技术领域
本发明属于新材料发明领域，具体材料为一种在含保护剂溶液中稳定的还原态贵金属孤原子材料。
背景技术
贵金属及其合金因其优良的性能成为现代工业中广泛应用的材料。由于其高温抗腐蚀性、高可靠性、高精度和长的使用寿命等特点，贵金属被广泛应用于航空航天、航海工业和军工用精密仪器制作中，如弹簧片、膜盒、导电游丝、轴尖等原件。同时，由于其材料生理上的无毒性、良好的延展性及生物相容性，贵金属被广泛应用于医学材料的制备中。比如在牙科领域中的汞齐合金和铸造合金两大主要牙用贵金属合金，医疗用金针、银针和硬针，医用电子器材电极材料等。再有，贵金属拥有独特的催化性能和稳定性，尤其是铂族金属(铱、铑、钯和铂)，其被广泛应用于石油化工，氢燃料电池等领域。然而贵金属资源的稀缺性以及制造工艺技术的落后使得贵金属的价格居高不下，严重制约了其在各个领域的充分利用。
贵金属孤原子为贵金属的利用提供了广阔的空间。Maria Flytzani-Stephanopoulos等(Acc.Chem.Res,2014,47,783.)报道了在各种不同的载体上Au单原子材料的合成，并将其成功的应用于水煤气变换反应。张涛等(Nature Chem.,2011,3,634.)报道了在氧化铁的表面Pt单原子材料的合成，并将其成功应用于一氧化碳的氧化反应，反应的转化频率提高了2-3倍。然而采用固体表面分散的方法得到的单原子材料不仅存在着载量低，不稳定等诸多问题，同时，由于固体表面与贵金属单原子的相互作用，贵金属单原子并不是以孤立状态存在的，其存在状态绑定于固体表面，与载体上的氧等作用力较强，金属中心并非为完全还原态(Nature Nanotechnology,2018，13,856；Nature Commu.,2019,10,234)，不易于从固体表面剥离，因而不能作为原料用于生成和制备更为广泛的物质。还原态的贵金属原子在溶液中运动的自由度大，极易聚集导致纳米粒子的产生，所以以溶液为介质分散还原态贵金属原子得到孤立状态的贵金属孤原子材料一直是科学技术领域的巨大挑战。乙烯基吡咯烷酮聚合物和异丙基丙烯酰胺聚合物等(J.Phys.Chem.B,1999,103,3818.；Langmuir 1997,13,6465.)。高分子聚合物被广泛应用于溶液中贵金属材料的合成，然而这些高分子聚合物很难阻止初始还原态的贵金属孤原子聚集长大成为纳米粒子。表面活性剂也被用于溶液中贵金属材料的合成，但是很难被除去，且被表面活性剂包裹的贵金属孤原子的自由度受限(专利号：201611004958.3)，另外残留在材料中的高分子聚合物、表面活性剂也会影响材料的应用特性。
基于以上的研究现状可知，如何既能克服依靠固体表面分散制备孤原子材料载量低，初始还原态贵金属孤原子易于聚集长大，以及体系中的保护剂难以去除等缺点，从而得到一种有效的制备稳定的还原态贵金属孤原子材料的方法具有重要的意义。
该发明中介绍了一种溶液中稳定的还原态贵金属孤原子材料和制备方法，该材料能稳定存在于含有保护基的溶剂中。这与文献中报道的金属有机化合物不同。Marc-Etienne Moret，Bele′n Gil等介绍了多种类型的金属配合物(Higher oxidation state organopalladium 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.如{[(C 6F 5) 3(tht)Pt]Ag(PPh 3)}(tht是tetrahydrothiophene),其结构中Pt，Ag金属键中两种金属均以离子的形式存在，即Pt(II)，Ag(I)，且金属中心周围有含磷、碳等配体。金属Pd原子配合物
Figure PCTCN2019111843-appb-000001
以及结构为
Figure PCTCN2019111843-appb-000002
的配合物中，金属中心周围有含氮、碳配体，以稳定其结构。
综上所述的金属配合物中，金属的价态为非还原态，且其结构中金属中心与含氮、磷或含碳配体形成金属-碳键、金属-氮或金属-磷键。即所报道的金属配合物是金属有机类化合物。这与该发明中介绍的一种溶液中稳定的金属孤原子材料不同。
本发明中的一种在溶液中稳定的还原态贵金属孤原子材料可用于材料制备、工业催化等领域。如还原态Pt孤原子材可应用在不饱和化合物的硅氢加成反应中(硅氢加成反应是指含有Si-H键的化合物与不饱和的有机化合物发生加成反应生成有机硅化合物的一类反应)。还原态Au孤原子材可应用在低温条件下一氧化碳氧化反应中等。另外该还原态贵金属孤原子材料，也可应用在材料镀层中。
发明内容
本发明的目的在于提供一种在溶液中稳定的还原态贵金属孤原子材料。
该材料由还原态的贵金属孤原子和保护剂组成，保护剂包含不限于链状醚类化合物。
该发明中所述的贵金属孤原子是指独立存在的，金属之间没有形成金属键，且贵金属的化学价态不高于正一价，为0价、或0价和正一价混合，优选为0价。对于常见价态中不含正一价的金属，如Pt，Pd等，溶液中该金属孤原子化学态为零价的比例至少占30％。对于常见价态中含正一价的金属，如银，溶液中该金属孤原子的化学态为零价的比例不低于80％.
所述的贵金属孤原子包含铂系元素、后铂系元素中的一种或二种以上，包含但不限于钯、铑、铱、钌、锇、铂、金中的一种或二种以上。
所述贵金属孤原子是铂原子或金原子。
所述的保护剂包含但不限于醚类结构的化合物中的一种或二种以上；所述的保护剂包含但不限于二醇醚类结构的化合物中的一种或二种以上；包含但不限于乙二醇醚类、丙二醇醚类结构的化合物中的一种或二种以上。
所述的保护剂包含但不限于乙二醇单甲醚，乙二醇二甲醚，乙二醇二乙基醚，丙二醇二甲基醚，二丙二醇二甲基醚，二乙二醇二甲醚，三乙二醇二甲醚，二乙二醇二***，三乙二醇二***，正丁醚中的一种或二种以上。
所述的贵金属孤原子与保护剂的摩尔比小于等于1：1，优选范围为10至10 6。
所述的贵金属孤原子的浓度范围为大于0至1mol/L。
所述的贵金属孤原子的浓度范围为0.01至50mmol/L。
该材料制备过程中成分组成包含但不限于链状醚类化合物、高氧化态的贵金属化合物前驱体、还原剂，或包含但不限于链状醚类化合物、高氧化态的贵金属化合物前驱体、还原剂、水；将所有组分按照所需比例充分混合成液体体系，反应后可以得到稳定存在的贵金属单原子溶液。
该材料制备过程中可包括以下三种情形中的一种或二种或三种使混合后的体系成液体；
第一种：成分组成中可包含水，水的质量浓度范围是0-70％，水可以作为溶剂组成；
第二种：成分组成中的链状醚类化合物包含在室温下为液体的保护剂时，液体链状醚类化合物可以作为溶剂组成；
第三种：成分组成中的还原剂包含在室温下为液体的还原剂时，液体还原剂可以作为溶剂组成。
所述高氧化态的贵金属化合物前驱体包含但不限于高氧化态的铂化合物前驱体(正二价、正四价中的一种或二种)、高氧化态的钯化合物前驱体(正二价、正四价中的一种或二种)、高氧化态的铑化合物前驱体(正三价)、高氧化态的铱化合物前驱体(正三价、正四价中的一种或二种)、高氧化态的钌化合物前驱体(正三价)、高氧化态的锇化合物前驱体(正二价、正三价、正四价中的一种或二种或三种)或高氧化态的金化合物前驱体(正三价)中的一种或二种以上。
所述高氧化态的贵金属化合物前驱体包含但不限于：氯金酸、氯金酸钠、氯金酸钾、氯金酸铵、氯铂酸、氯铂酸钠、氯铂酸钾、氯化亚铂、氯化铂、亚氯铂酸钾、亚氯铂酸钠、二乙胺氯化铂、硝酸铂、1,5-环辛二烯二氯化铂、三氯(乙烯)合铂酸钾、二氯四氨合铂、二腈苯基二氯合铂、二(亚磷酸三苯酯)二氯化铂、四氯铂酸铵、氯钯酸铵、氯钯酸钠、氯钯酸钾、氯铑酸铵、氯铑酸钠、氯铑酸钾、氯铱酸、氯铱酸钠、氯铱酸钾、氯铱酸铵中的一种或二种以上。
所述还原剂包含但不限于醇类化合物、葡萄糖、甲酸、柠檬酸、酒石酸、抗坏血酸、水合肼或硼氢化物中的一种或二种以上混合物。
所述醇类化合物还原剂包含但不限于甲醇、乙醇、丙醇、异丙醇、正丁醇，异丁醇，仲丁醇，叔丁醇、乙二醇，丙三醇中的一种或二种以上混合物。
本发明提供了一种溶液中稳定的还原态贵金属孤原子的材料。由还原态贵金属孤原子和保护剂组成。以含有醚键基团的链状化合物为保护剂，使还原态贵金属孤原子稳定存在。本发明系首次采用链状醚类化合物为保护剂，在溶液中制得贵金属孤原子材料，避免了合成过程中初级孤原子的聚积导致纳米粒子的产生。该材料的还原态孤原子区别于金属纳米粒子，可用于能源材料、医药合成、医疗材料、催化剂制备等领域。也为数目可控的同种或异种金属团簇、纳米材料的合成提供了基础孤原子原料。
附图说明
图1为实施例1,8,9,10的紫外可见图谱
图2为实施例1,3,4,5,6,7,8,9,10的195PtNMR谱图
图3为实施例2,12的紫外可见图谱
图4为实施例3的紫外可见图谱
图5为实施例4的紫外可见图谱
图6为实施例5的紫外可见图谱
图7为实施例6的紫外可见图谱
图8为实施例7的紫外可见图谱
图9为实施例11的紫外可见图谱
图10为实施例13的高分辨球差矫正扫描透射电子显微镜分析图之一
图11为实施例13的高分辨球差矫正扫描透射电子显微镜分析图之二
图12为实施例14的高分辨球差矫正扫描透射电子显微镜分析图。
具体实施方式
下面以在溶液中稳定的铂、金、依孤原子材料为例对本发明做进一步的详细说明。
本专利的保护内容并不以具体实施方式为限，而是由权利要求限制。
实施例1
溶液中铂孤原子的制备：将67ml乙二醇二***，67ml乙醇，10.2ml水以及4.8ml浓度为0.018mol/L氯铂酸溶液充分混合，然后升温，在75℃下冷凝回流24小时使氯铂酸完全还原。用减压蒸馏的方法即可将溶液中的乙醇和乙二醇二***除去。经紫外和195Pt NMR检测可知合成得到了铂孤原子材料。紫外可见吸收光谱图(图1)表明：氯铂酸被完全还原。(说明：在制备过程中，用紫外光谱分析仪分析PtCl62-离子峰的吸收强度随时间的变化，如图1所示。在265nm处的紫外吸收峰代表PtCl62-的吸收峰。随着时间的延长，该紫外吸收峰的强度逐渐减弱至消失(从上到下)，说明氯铂酸逐渐被还原至完全还原)。195Pt NMR谱图(图2)表明：还原态的铂孤原子形成。(说明：K2PtCl6的195Pt NMR在0ppm处，PtCl42-的峰在-1617ppm处，而Pt孤原子的195Pt NMR峰在-2755ppm处，同时并没有检测到铂纳米粒子的纳特位移大宽峰:-35000ppm到10000ppm，这说明H2PtCl6完全还原且Pt孤原子生成，同时没有Pt纳米粒子产生)，240h之后再分析，结果保持不变。
实施例2
溶液中金孤原子的制备：将67ml乙二醇二***，67ml乙醇，10.2ml水以及3ml浓度为0.0243mol/L氯金酸溶液充分混合，然后升温，在80℃下冷凝回流24小时使氯金酸完全还原。紫外可见吸收光谱图(图3)表明：氯金酸被完全还原。240h之后再分析，结果保持不变。(说明：在制备过程中，用紫外光谱分析仪分析AuCl4-离子峰的吸收强度随时间的变化，如图3所示。在322nm处的紫外吸收峰代表AuCl4-离子的吸收峰。随着时间的延长，该紫外吸收峰的强度逐渐减弱(从上到下)，说明氯金酸逐渐被还原)。用减压蒸馏的方法即可将溶液中的乙醇和乙二醇二***除去。
实施例3
溶液中铂孤原子的制备：将60ml丙二醇二甲醚，60ml乙醇，10ml水以及4.8ml浓度为0.018mol/L氯铂酸溶液充分混合，然后升温，在75℃下冷凝回流14小时使氯铂酸完全还原。经紫外和195Pt NMR检测可知合成得到了铂孤原子材料。紫外可见吸收光谱图如图4所示。(说明：在制备过程中，用紫外光谱分析仪分析PtCl62-离子峰的吸收强度随时间的变化，如图4所示。在265nm处的紫外吸收峰代表PtCl62-的吸收峰。随着时间的延长，该紫外吸收峰的强度逐渐减弱至消失(从上到下)，说明氯铂酸逐渐被还原至完全还原)。195Pt NMR谱图与图2相同。240h之后再分析，结果保持不变。(说明：K2PtCl6的195Pt NMR在0ppm处，PtCl42-的峰在-1617ppm处， 而Pt孤原子的195Pt NMR峰在-2755ppm处，同时并没有检测到铂纳米粒子的纳特位移大宽峰:-35000ppm到10000ppm，这说明H2PtCl6完全还原且Pt孤原子生成，同时没有Pt纳米粒子产生)。
实施例4
溶液中铂孤原子的制备：将60ml乙二醇二甲醚，60ml乙醇，10ml水以及4.8ml浓度为0.018mol/L氯铂酸溶液充分混合，然后升温，在75℃下冷凝回流16.5h使氯铂酸完全还原。经紫外和195Pt NMR检测可知合成得到了铂孤原子材料。紫外可见吸收光谱图(图5)表明：氯铂酸被完全还原。(说明：在制备过程中，用紫外光谱分析仪分析PtCl62-离子峰的吸收强度随时间的变化，如图5所示。在265nm处的紫外吸收峰代表PtCl62-的吸收峰。随着时间的延长，该紫外吸收峰的强度逐渐减弱至消失(从上到下)，说明氯铂酸逐渐被还原至完全还原)其195Pt NMR谱图与图2所示相同。(说明：K2PtCl6的195Pt NMR在0ppm处，PtCl42-的峰在-1617ppm处，而Pt孤原子的195Pt NMR峰在-2755ppm处，同时并没有检测到铂纳米粒子的纳特位移大宽峰:-35000ppm到10000ppm，这说明H2PtCl6完全还原且Pt孤原子生成，同时没有Pt纳米粒子产生)。
实施例5
溶液中铂孤原子的制备：将60ml二乙二醇二甲醚，60ml乙醇，10ml水以及4.8ml浓度为0.018mol/L氯铂酸溶液充分混合，然后升温，在75℃下冷凝回流3.5h使氯铂酸完全还原。经紫外和195Pt NMR检测可知合成得到了铂孤原子材料。紫外可见吸收光谱图(图6)表明：氯铂酸被完全还原。(说明：在制备过程中，用紫外光谱分析仪分析PtCl62-离子峰的吸收强度随时间的变化，如图6所示。在265nm处的紫外吸收峰代表PtCl62-的吸收峰。随着时间的延长，该紫外吸收峰的强度逐渐减弱至消失(从上到下)，说明氯铂酸逐渐被还原至完全还原)。其195Pt NMR谱图与图2所示相同。(说明：K2PtCl6的195Pt NMR在0ppm处，PtCl42-的峰在-1617ppm处，而Pt孤原子的195Pt NMR峰在-2755ppm处，同时并没有检测到铂纳米粒子的纳特位移大宽峰:-35000ppm到10000ppm，这说明H2PtCl6完全还原且Pt孤原子生成，同时没有Pt纳米粒子产生)。
实施例6
溶液中铂孤原子的制备：将50ml乙二醇单甲醚，50ml乙醇，7ml水以及3.5ml浓度为0.018mol/L氯铂酸溶液充分混合，然后升温，在75℃下冷凝回流9.3h使氯铂酸完全还原。经紫外和195Pt NMR检测可知合成得到了铂孤原子材料。紫外可见吸收光谱图(图7)表明：氯铂酸被完全还原。(说明：在制备过程中，用紫外光谱分析仪分析PtCl62-离子峰的吸收强度随时间的变化，如图7所示。在265nm处的紫外吸收峰代表PtCl62-的吸收峰。随着时间的延长，该紫外吸收峰的强度逐渐减弱至消失(从上到下)，说明氯铂酸逐渐被还原至完全还原)。其195Pt NMR谱图与图2所示相同。(说明：K2PtCl6的195Pt NMR在0ppm处，PtCl42-的峰在-1617ppm处，而Pt孤原子的195Pt NMR峰在-2755ppm处，同时并没有检测到铂纳米粒子的纳特位移大宽峰:-35000ppm到10000ppm，这说明H2PtCl6完全还原且Pt孤原子生成，同时没有Pt纳米粒子产生)。
实施例7
溶液中铂孤原子的制备：将75ml丁醚，35ml乙醇，7.5ml水以及3.5ml浓度为0.018mol/L氯铂酸溶液充分混合，然后升温，在75℃下冷凝回流5h使氯铂酸完全还原。经紫外和195Pt NMR检测可知合成得到了铂孤原子材料。紫外可见吸收光谱图(图8)表明：氯铂酸被完全还原。(说明：在制备过程中，用紫外光谱分析仪分析PtCl62-离子峰的吸收强度随时间的变化，如图5所示。在265nm处的紫外吸收峰代表PtCl62-的吸收峰。随着时间的延长，该紫外吸收峰的强度逐渐减弱至消失(从上到下)，说明氯铂酸逐渐被还原至完全还原)。其195Pt NMR谱图与图2所示相同。(说明：K2PtCl6的195Pt NMR在0ppm处，PtCl42-的峰在-1617ppm处，而Pt孤原子的195Pt NMR峰在-2755ppm处，同时并没有检测到铂纳米粒子的纳特位移大宽峰:-35000ppm到10000ppm，这说明H2PtCl6完全还原且Pt孤原子生成，同时没有Pt纳米粒子产生)。
实施例8
溶液中铂孤原子的制备：将469ml乙醇，6.7ml乙二醇二***(乙醇与乙二醇二***物质量的比为130:1)，0.1ml水(乙醇与水的物质的量比例为1500:1)以及0.48ml浓度为0.018mol/L氯铂酸溶液(乙醇与Pt的物质量的比为10 6:1)充分混合，然后升温，在室温下搅拌600小时使氯铂酸完全还原。经紫外和 195Pt NMR检测可知合成得到了铂孤原子材料。240h之后再分析，结果保持不变。其紫外可见图谱与图1所示各谱线趋势相同，图谱相似(说明：在制备过程中，用紫外光谱分析仪分析PtCl 6 2-离子峰的吸收强度随时间的变化。在265nm处的紫外吸收峰代表PtCl 6 2-的吸收峰。随着时间的延长，该紫外吸收峰的强度逐渐减弱至消失(从上到下)，说明氯铂酸逐渐被还原至完全还原)；其 195PtNMR谱图与图2相同。(说明：K 2PtCl 6的 195Pt NMR在0ppm处，PtCl 4 2-的峰在-1617ppm处，而Pt孤原子的 195Pt NMR峰在-2755ppm处，同时并没有检测到铂纳米粒子的纳特位移大宽峰:-35000ppm到10000ppm，这说明H 2PtCl 6完全还原且Pt孤原子生成，同时没有Pt纳米粒子产生)。
实施例9
溶液中铂孤原子的制备：将7ml乙醇，67ml乙二醇二***(乙醇与乙二醇二***物质量的比为0.18:1)，1ml水(乙醇与水的物质的量比例为0.01:1)以及4.8ml浓度为0.018mol/L氯铂酸溶液(乙醇与Pt的物质量的比为10:1)充分混合，然后升温，在室温下搅拌600小时使氯铂酸完全还原。经紫外和 195Pt NMR检测可知合成得到了铂孤原子材料。240h之后再分析，结果保持不变。其紫外可见图谱与图1所示各谱线趋势相同，图谱相似，(说明：在制备过程中，用紫外光谱分析仪分析PtCl 6 2-离子峰的吸收强度随时间的变化，如图1所示。在265nm处的紫外吸收峰代表PtCl 6 2-的吸收峰。随着时间的延长，该紫外吸收峰的强度逐渐减弱至消失(从上到下)，说明氯铂酸逐渐被还原至完全还原)。其 195PtNMR谱图与图2相同。(说明：K 2PtCl 6的 195Pt NMR在0ppm处，PtCl 4 2-的峰在-1617ppm处，而Pt孤原子的 195Pt NMR峰在-2755ppm处，同时并没有检测到铂纳米粒子的纳特位移大宽峰:-35000ppm到10000ppm，这说明H 2PtCl 6完全还原且Pt孤原子生成，同时没有Pt纳米粒子产生)。
实施例10
溶液中铂孤原子的制备：将6.7ml乙醇，6.7ml乙二醇二***，1ml水以及4.8ml浓度为0.018mol/L氯铂酸溶液充分混合，然后升温，在室温下搅拌600小时使氯铂 酸完全还原。经紫外和 195Pt NMR检测可知合成得到了铂孤原子材料。240h之后再分析，结果保持不变。其紫外可见图谱与图1所示各谱线趋势相同，图谱相似，(说明：在制备过程中，用紫外光谱分析仪分析PtCl 6 2-离子峰的吸收强度随时间的变化。在265nm处的紫外吸收峰代表PtCl 6 2-的吸收峰。随着时间的延长，该紫外吸收峰的强度逐渐减弱至消失(从上到下)，说明氯铂酸逐渐被还原至完全还原)。其 195PtNMR谱图与图2相同。(说明：K 2PtCl 6的 195Pt NMR在0ppm处，PtCl 4 2-的峰在-1617ppm处，而Pt孤原子的 195Pt NMR峰在-2755ppm处，同时并没有检测到铂纳米粒子的纳特位移大宽峰:-35000ppm到10000ppm，这说明H 2PtCl 6完全还原且Pt孤原子生成，同时没有Pt纳米粒子产生)。
实施例11
溶液中铱孤原子的制备：将67ml乙二醇二***，67ml乙醇，10.2ml水以及3ml浓度为0.0243mol/L氯铱酸溶液充分混合，然后升温，在70℃下冷凝回流8小时使氯铱酸完全还原。其紫外可见吸收光谱图(图9)表明：氯铱酸被完全还原。240h之后再分析，结果保持不变。(说明：绿色线的紫外吸收峰代表IrCl 6 -离子的吸收峰，随着时间的延长，该紫外吸收峰的强度逐渐减弱至消失(从上到下)，说明氯铱酸逐渐被完全还原)。
实施例12
溶液中金孤原子的制备：将67ml乙二醇二***，67ml乙醇，10.2ml水以及3ml浓度为0.0243mol/L氯金酸溶液充分混合，然后升温，在80℃下冷凝回流24小时使氯金酸完全还原。紫外可见吸收光谱图(与图3所示各谱线趋势相同)表明：氯金酸被完全还原。240h之后再分析，结果保持不变。((说明：在322nm处的紫外吸收峰代表AuCl 4 -离子的吸收峰，在制备过程中，用紫外光谱分析仪分析AuCl 4 -离子峰的吸收强度随时间的变化。如图3所示，随着时间的延长，该紫外吸收峰的强度逐渐减弱(从上到下)，说明氯金酸逐渐被还原)。将不锈钢片(2cm*3cm)，放至上述制得的金孤原子溶液中，2小时后，可以得到表面被镀金的不锈钢片。
实施例13
金孤原子催化剂的制备：
取150ml实施例2中制备的金孤原子溶液，向其中加约1.7g氧化钛，除去溶剂后，可得到1wt％Au/TiO 2,高分辨球差矫正扫描透射电子显微镜分析(图10，图11,放大倍数不同，且所选的区域也不相同,结果是一样的)可知，所得样品中Au以单个原子的形式存在。
实施例14
铂孤原子催化剂的制备：
取150ml实施例1中制备的铂孤原子溶液，向其中加约1.7g氧化钛，除去溶剂后，可得到1wt％Pt/TiO 2,高分辨球差矫正扫描透射电子显微镜分析(图12)可知，所得样品中Pt以单个原子的形式存在。

Claims (17)

  1. 一种溶液中稳定的还原态贵金属孤原子材料，其特征在于：该材料包括还原态的贵金属孤原子和保护剂、或由还原态的贵金属孤原子和保护剂组成，保护剂包含但不限于链状醚类化合物。
  2. 按照权利要求1所述的一种溶液中稳定的还原态贵金属孤原子材料，其特征在于：所述的贵金属孤原子的化学价态不高于正一价，其为0价、或0价和正一价混合，优选为0价。
  3. 按照权利要求1所述的一种溶液中稳定的还原态贵金属孤原子材料，其特征在于：所述的贵金属孤原子包含铂系元素、后铂系元素中的一种或二种以上，包含但不限于钯、铑、铱、钌、锇、铂、金中的一种或二种以上。
  4. 按照权利要求1所述的一种溶液中稳定的还原态贵金属孤原子材料，其特征在于：所述贵金属孤原子是铂原子或金原子。
  5. 按照权利要求1所述的一种溶液中稳定的还原态贵金属孤原子材料，其特征在于：所述的保护剂包含但不限于醚类结构的化合物中的一种或二种以上；所述的保护剂包含但不限于二醇醚类结构的化合物中的一种或二种以上；优选包含但不限于乙二醇醚类、丙二醇醚类结构的化合物中的一种或二种以上。
  6. 按照权利要求1或5所述的一种溶液中稳定的还原态贵金属孤原子材料，其特征在于：所述的保护剂包含但不限于乙二醇单甲醚，乙二醇二甲醚，乙二醇二乙基醚，丙二醇二甲基醚，二丙二醇二甲基醚，二乙二醇二甲醚，三乙二醇二甲醚，二乙二醇二***，三乙二醇二***，正丁醚中的一种或二种以上。
  7. 按照权利要求1所述的一种溶液中稳定的还原态贵金属孤原子材料，其特征在于：所述的贵金属孤原子与保护剂的摩尔比小于等于1：1，优选范围为10至10 6。
  8. 按照权利要求1或7所述的一种溶液中稳定的还原态贵金属孤原子材料，其特征在于：所述的贵金属孤原子的浓度范围为大于0至1mol/L，优先范围为0.01至50mmol/L。
  9. 一种权利要求1-8任一所述溶液中稳定的还原态贵金属孤原子材料的制备方法，其特征在于：该材料制备过程中成分组成包含但不限于链状醚类化合物、高氧化态的贵金属化合物前驱体、还原剂，或包含但不限于链状醚类化合物、高氧化态的贵金属化合物前驱体、还原剂、水；
    将所有组分按照所需比例充分混合成液体体系，反应后可以得到稳定存在的贵金属单原子溶液。
  10. 按照权利要求9所述一种溶液中稳定的还原态贵金属孤原子材料的制备方法，其特征在于：
    该材料制备过程中可包括以下三种情形中的一种或二种或三种使混合后的体系成液体；
    第一种：成分组成中可包含水，水的质量浓度范围是0-70％，水可以作为溶剂组成；
    第二种：成分组成中的链状醚类化合物包含在室温下为液体的保护剂时，液体链状醚类化合物可以作为溶剂组成；
    第三种：成分组成中的还原剂包含在室温下为液体的还原剂时，液体还原剂可以作为溶剂组成。
  11. 按照权利要求9所述的一种溶液中稳定的还原态贵金属孤原子材料的制备方法，其特征在于：所述高氧化态的贵金属化合物前驱体包含但不限于高氧化态的铂化合物前驱体(贵金属正二价、正四价中的一种或二种)、高氧化态的钯化合物前驱体(贵金属正二价、正四价中的一种或二种)、高氧化态的铑化合物前驱体(贵金属正三价)、高氧化态的铱化合物前驱体(贵金属正三价、正四价中的一种或二种)、高氧化态的钌化合物前驱体(贵金属正三价)、高氧化态的锇化合物前驱体(贵金属正二价、正三价、正四价中的一种或二种或三种)或高氧化态的金化合物前驱体(贵金属正三价)中的一种或二种以上。
  12. 按照权利要求9所述的一种溶液中稳定的还原态贵金属孤原子材料的制备方法，其特征在于：所述高氧化态的贵金属化合物前驱体包含但不限于：氯金酸、氯金酸钠、氯金酸钾、氯金酸铵、氯铂酸、氯铂酸钠、氯铂酸钾、氯化亚铂、氯化铂、亚氯铂酸钾、亚氯铂酸钠、二乙胺氯化铂、硝酸铂、1,5-环辛二烯二氯化铂、三氯(乙烯)合铂酸钾、二氯四氨合铂、二腈苯基二氯合铂、二(亚磷酸三苯酯)二氯化铂、四氯铂酸铵、氯钯酸铵、氯钯酸钠、氯钯酸钾、氯铑酸铵、氯铑酸钠、氯铑酸钾、氯铱酸、氯铱酸钠、氯铱酸钾、氯铱酸铵中的一种或二种以上。
  13. 按照权利要求9所述的一种溶液中稳定的还原态贵金属孤原子材料的制备方法，其特征在于：所述还原剂包含但不限于醇类化合物、葡萄糖、甲酸、柠檬酸、酒石酸、抗坏血酸、水合肼或硼氢化物中的一种或二种以上混合物。
  14. 按照权利要求13所述的一种溶液中稳定的还原态贵金属孤原子材料的制备方法，其特征在于：所述醇类化合物还原剂包含但不限于甲醇、乙醇、丙醇、异丙醇、正丁醇、异丁醇、仲丁醇、叔丁醇、乙二醇、丙三醇中的一种或二种以上混合物。
  15. 按照权利要求9所述的一种溶液中稳定的还原态贵金属孤原子材料的制备方法，其特征在于：反应的温度范围为室温至200℃，优选50至100℃。
  16. 按照权利要求9所述的一种溶液中稳定的还原态贵金属孤原子材料的制备方法，其特征在于：反应的时间范围在0.5h至600h，优选4h至50h。
  17. 按照权利要求9所述的一种溶液中稳定的还原态贵金属孤原子材料的制备方法，其特征在于：所述的还原剂和高氧化态贵金属前驱物的物质的量比例变化范围为：1-10 7，优选10 2-10 6。
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