WO2018085958A1 - 一种在溶液中稳定的贵金属孤原子材料 - Google Patents

一种在溶液中稳定的贵金属孤原子材料 Download PDF

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WO2018085958A1
WO2018085958A1 PCT/CN2016/000652 CN2016000652W WO2018085958A1 WO 2018085958 A1 WO2018085958 A1 WO 2018085958A1 CN 2016000652 W CN2016000652 W CN 2016000652W WO 2018085958 A1 WO2018085958 A1 WO 2018085958A1
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noble metal
platinum
solution
atom
stable
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PCT/CN2016/000652
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French (fr)
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张宗超
刘凯瑞
毛璟博
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中国科学院大连化学物理研究所
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Priority to JP2019524402A priority Critical patent/JP6928214B2/ja
Priority to KR1020197016691A priority patent/KR20190091280A/ko
Priority to US16/349,178 priority patent/US20190329225A1/en
Priority to CA3045346A priority patent/CA3045346A1/en
Priority to EP16921311.3A priority patent/EP3539656A4/en
Publication of WO2018085958A1 publication Critical patent/WO2018085958A1/zh

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Definitions

  • the invention belongs to the field of new material invention, and the specific material is a noble metal orphan atom material which is stable in solution.
  • precious metals and their alloys have become widely used materials in modern industry 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 aerospace, marine industry and military precision instruments, such as spring sheets, bellows, conductive hairsprings, shafts. Sharp and other originals. At the same time, precious metals are widely used in the preparation of medical materials due to their physiological non-toxicity, good ductility and biocompatibility. For example, amalgam alloys and casting alloys in the dental field are two major precious metal alloys for dental use, medical gold needles, silver needles and hard needles, and medical electronic equipment electrode materials.
  • precious metals possess unique catalytic properties and stability, especially platinum group metals (ruthenium, osmium, palladium and platinum), which are widely used in petrochemical, hydrogen fuel cells and other fields.
  • platinum group metals ruthenium, osmium, palladium and platinum
  • the scarcity of precious metal resources and the backwardness of manufacturing technology make the price of precious metals remain high, which seriously restricts their full use in various fields.
  • the noble metal atoms provide a broad space for the use of precious metals.
  • Maria Flytzani-Stephanopoulos et al. (Acc. Chem. Res, 2014, 47, 783.) reported the synthesis of Au monoatomic materials on a variety of different supports and successfully applied them to water gas shift reactions.
  • Zhang Tao 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. The conversion frequency of the reaction was increased by 2-3 times.
  • the monoatomic material obtained by the solid surface dispersion method not only has many problems such as low loading and instability, but also the noble metal single atom is not isolated due to the interaction of the solid surface with the noble metal single atom.
  • the state in which it exists is bound to a solid surface and is not easily peeled off from the solid surface, and thus cannot be used as a raw material for the production and preparation of a wider range of substances.
  • the noble metal atoms in the reduced state have a large degree of freedom of movement in the solution, and are easily aggregated to cause the generation of nanoparticles. Therefore, it is a great challenge in the field of science and technology to obtain a noble metal atomic material in an isolated state by dispersing a reduced metal atom in a solution.
  • Vinylpyrrolidone polymers and isopropylacrylamide polymers (J. Phys. Chem. B, 1999, 103, 3818.; Langmuir 1997, 13, 6465.) Polymers are widely used in precious metal materials in solution. However, these high molecular polymers cannot prevent the accumulation of noble metal atoms in the initial reduced state from growing into nanoparticles, so the successful synthesis of the reduced noble metal atoms in solution has not been reported so far.
  • the noble metal atomic material stabilized in the solution provided by the invention is composed of a noble metal atom and a protective agent.
  • the noble metal atom is a platinum element or a post platinum element; the platinum element is palladium, rhodium, ruthenium, osmium, iridium or platinum; and the post platinum element is silver or gold.
  • the noble metal atom is platinum; the nuclear magnetic signal of the isotope having a platinum atomic mass of 195 is mainly characterized by between -2600 and -2800 ppm.
  • the protective agent is a block copolymer containing a siloxy group and a hydrophilic polymer.
  • the protective agent is a block copolymer containing a siloxy group and a polyether group.
  • a polysiloxane-polyglycol compound is preferred.
  • polysiloxane-polyglycol compounds a polysiloxane-polyethylene glycol block copolymer is preferred, and its structural formula is as follows:
  • the noble metal atom may account for any proportion of the weight of the protective agent.
  • the mass ratio of the noble metal atom to the protective agent is preferably 0.001%-50%.
  • a method for preparing a stable noble metal orphan atom material in a solution which is characterized in that the following steps are carried out: a block copolymer containing a siloxy group and a polyether group, a noble metal compound precursor, a reducing agent, and water are used. Mixing in a certain proportion; at -30-200 ° C, after 0.5-200 h of reaction, the reducing agent in the solution reduces the noble metal compound precursor to a monovalent noble metal mono atom, thereby obtaining a noble metal monoatomic solution which can exist stably;
  • the ratio of the amount of the reducing agent to the precursor of the noble metal compound precursor ranges from 1.0 to 10 7 times.
  • the ratio of the amount of the reducing agent and the water substance varies: 1:10 5 -30:1.
  • the noble metal compound precursor accounts for any ratio of the weight of the protective agent.
  • the noble metal compound precursor comprises: chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate, platinum chloride, platinum chloride, platinum chloride, platinum nitrate, 1,5-cyclooctadiene Platinum chloride, trichloro(ethylene)platinic acid, potassium tetraammine platinum, dinitrile phenyl dichloroplatinum, bis(triphenyl phosphite) platinum dichloride or tetrachloroplatinic acid One of the ammonium.
  • the reducing agent is one of an alcohol compound, glucose, formic acid, citric acid, tartaric acid, ascorbic acid, hydrazine hydrate or borohydride.
  • the alcohol compound is one or a mixture of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, ethylene glycol, glycerol.
  • the invention achieves for the first time the preparation of a noble metal atom in a reduced state in a solution phase. Compared with the synthesis of the metal material in the conventional solution phase, the formation of the metal nanoparticles is avoided, and a reduced-state orphan atom solution in the form of a single metal atom is obtained. Compared with the solid atomic material supported on the solid surface, it has high load capacity and good stability.
  • 195 Pt NMR spectrum indicates: reduced state Platinum is formed by an atom.
  • 195 Pt NMR of K 2 PtCl 6 is at 0 ppm
  • peak of PtCl 4 2- is at -1617 ppm
  • 195 Pt NMR peak of Pt orphaned atom is at -2680 ppm, and no nanoparticle of platinum nanoparticles is detected.
  • the large displacement peak of the special displacement -35000ppm to 10000ppm, which means that H 2 PtCl 6 is completely reduced and Pt is formed by atoms, and no Pt nanoparticles are produced.

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Abstract

一种溶液中稳定贵金属孤原子的材料，由贵金属孤原子和保护剂组成。以含有硅氧基团以及聚醚基团的嵌段共聚物为保护剂，使还原态贵金属孤原子稳定存在。材料制备过程中可用含还原剂的水溶液为溶剂。其中贵金属可占保护剂重量的任意比例。通过采用保护剂，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已知金属纳米粒子，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。

Description

一种在溶液中稳定的贵金属孤原子材料 技术领域
本发明属于新材料发明领域，具体材料为一种在溶液中稳定的贵金属孤原子材料。
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，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无法阻止初始还原态的贵金属孤原子聚集长大成为纳米粒子，所以溶液中还原态贵金属孤原子的成功合成至今仍无人报道。
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，不稳定等缺点，又能消除溶液中初始还原态贵金属孤原子聚集长大的趋势，从而得到一种有效的制备贵金属孤原子材料的方法具有重要的意义。
发明内容
本发明的目的在于提供一种在溶液中稳定的贵金属孤原子材料。
本发明提供的一种在溶液中稳定的贵金属孤原子材料由贵金属孤原子和保护剂组成。
所述的贵金属孤原子为铂系元素或后铂系元素；所述铂系元素为钯、铑、铱、钌、锇或铂；所述后铂系元素为银或金。
所述的的贵金属孤原子为铂；以铂元素原子质量为195的同位素的核磁信号在-2600和-2800ppm之间为主要特征。
所述的保护剂是含有硅氧基团以及亲水聚合物的嵌段共聚物。
所述的保护剂是含有硅氧基团以及聚醚基团的嵌段共聚物。
所述的含有硅氧基团以及聚醚基团的嵌段共聚物中优选聚硅氧烷-聚二醇类化合物。
所述的聚硅氧烷-聚二醇类化合物中优选聚硅氧烷-聚乙二醇嵌段共聚物，其结构式如下：
Figure PCTCN2016000652-appb-000001
所述的贵金属孤原子可占保护剂重量的任意比例。
所述的贵金属孤原子占保护剂的质量比优选0.001％-50％.
一种溶液中稳定的贵金属孤原子材料的制备方法，其特征在于按照以下步骤进行：将含有硅氧基团以及聚醚基团的嵌段共聚物，贵金属化合物前驱体，和还原剂、水按照一定比例充分混合；在-30-200℃下，反应0.5-200h后溶液中的还原剂将贵金属化合物前驱体还原为零价的贵金属单原子，从而得到能够稳定存在的贵金属单原子溶液；
所述的还原剂和贵金属化合物前驱体的物质的量比例变化范围为：1.0-107倍。
所述的还原剂和水的物质的量比例变化范围为：1∶105-30∶1。
所述的贵金属化合物前驱体占保护剂重量任意比。
所述贵金属化合物前驱体包括：氯铂酸、氯铂酸钠、氯铂酸钾、氯化亚铂、氯化铂、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)二氯化铂或四氯铂酸 铵中的一种。
所述还原剂为醇类化合物、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。
所述醇类化合物为甲醇、乙醇、丙醇、异丙醇、正丁醇，异丁醇，仲丁醇，叔丁醇、乙二醇，丙三醇中的一种或几种混合物。
本发明首次实现了在溶液相中还原态贵金属孤原子的制备。相对于传统的溶液相中金属材料的合成而言，避免了金属纳米粒子的形成，得到以孤个金属原子形式存在的还原态孤原子溶液。相对于固体表面负载的孤原子材料而言，其具有载量高，稳定性好的特点。
附图说明
图1，实施例1，2，3，4，5，6的紫外可见图谱。
图2为实施例1，2，3，4，5，6的195PtNMR谱图。
具体实施方式
下面以在溶液中稳定的铂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0.6465g聚乙二醇-聚硅氧烷嵌段共聚物，135ml乙醇，10.2ml水以及4.8ml浓度为0.018404mol/L氯铂酸溶液充分混合，然后升温，在105℃下冷凝回流3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(图1)表明：氯铂酸被完全还原。(说明：在265nm处的紫外吸收峰代表PtCl6 2-离子的吸收峰，而该紫外吸收峰的消失说明氯铂酸被完全还原。)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，PtCl4 2-的峰在-1617ppm 处，而Pt孤原子的195Pt NMR峰在-2680ppm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2
溶液中铂孤原子的制备：将0.6465g聚乙二醇-聚硅氧烷嵌段共聚物，4.05mg乙醇(乙醇与氯铂酸物质的量之比为1∶1)，145ml水以及4.8ml浓度为0.018404mol/L氯铂酸溶液充分混合(乙醇与水的物质的量比例为1∶105)，然后升温，在105℃下冷凝回流3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。紫外可见图谱如图1所示，195PtNMR谱图如图2所示。
实施例3
溶液中铂孤原子的制备：将0.6465g聚乙二醇-聚硅氧烷嵌段共聚物，148.5ml乙醇，1.02ml水以及0.48ml浓度为0.18404mol/L氯铂酸溶液充分混合(乙醇与水的物质的量比例为30∶1)，然后升温，在105℃下冷凝回流3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。紫外可见图谱如图1所示，195PtNMR谱图如图2所示。
实施例4
溶液中铂孤原子的制备：将0.6465g聚乙二醇-聚硅氧烷嵌段共聚物，882g乙醇(1.14L，乙醇加入量为氯铂酸物质的量的107倍)，100.2ml水以及4.8ml浓度为0.018404mol/L氯铂酸溶液充分混合，然后升温，在105℃下冷凝回流3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。紫外可见图谱如图1所示，195PtNMR谱图如图2所示。
实施例5
溶液中铂孤原子的制备：将1719.92g聚乙二醇-聚硅氧烷嵌段共聚物，1000ml乙醇，100ml水以及4.8ml浓度为0.018404mol/L氯铂酸溶液充分混合(铂孤原子占保护剂质量的0.001％)，然后升温，在105℃下冷凝回流3小时使氯铂酸完全还原。紫外可见图谱如图1所示，195PtNMR谱图如图2所示。
实施例6
溶液中铂孤原子的制备：将0.0344g聚乙二醇-聚硅氧烷嵌段共聚物，135ml乙醇，10.2ml水以及4.8ml浓度为0.018404mol/L氯铂酸溶液充分混合(铂孤原子占保护剂质量的50％)，然后升温，在105℃下冷凝回流3小时使氯铂酸完全还原。紫外可见图谱如图1所示，195PtNMR谱图如图2所示。

Claims (12)

  1. 一种溶液中稳定的贵金属孤原子材料，其特征在于该材料由贵金属孤原子和保护剂组成。
  2. 按照权利要求1所述的一种溶液中稳定的贵金属孤原子材料，其特征在于所述的贵金属孤原子为铂系元素或后铂系元素；所述铂系元素为钯、铑、铱、钌、锇或铂；所述后铂系元素为银或金。
  3. 按照权利要求1所述的一种溶液中稳定的贵金属孤原子材料，其特征在于所述的的贵金属孤原子为铂；以铂元素原子质量为195的同位素的核磁信号在-2600和-2800ppm之间为主要特征。
  4. 按照权利要求1所述的一种溶液中稳定的贵金属孤原子材料，其特征在于所述的保护剂是含有硅氧基团以及亲水聚合物的嵌段共聚物。
  5. 按照权利要求1所述的一种溶液中稳定的贵金属孤原子材料，其特征在于所述的保护剂是含有硅氧基团以及聚醚基团的嵌段共聚物。
  6. 按照权利要求5所述的一种溶液中稳定的贵金属孤原子材料，其特征在于所述的含有硅氧基团以及聚醚基团的嵌段共聚物中优选聚硅氧烷-聚二醇类化合物。
  7. 按照权利要求6所述的一种溶液中稳定的贵金属孤原子材料，其特征在于所述的聚硅氧烷-聚二醇类化合物中优选聚硅氧烷-聚乙二醇嵌段共聚物，其结构式如下
    Figure PCTCN2016000652-appb-100001
  8. 按照权利要求1所述的一种溶液中稳定的贵金属孤原子材料，其特征在于所述的贵金属孤原子可占保护剂质量的任意比。
  9. 一种溶液中稳定的贵金属孤原子材料的制备方法，其特征在于按照以下步骤进行：将含有硅氧基团以及聚醚基团的嵌段共聚物，贵金属化合物前驱体，和还原剂、水按照一定比例充分混合；在-30-200℃下，反应0.5-200h得到贵金属孤原子，从而得到能够稳定存在的贵金属单原子溶液；
    所述的还原剂和贵金属化合物前驱体的物质的量比例变化范围为：1-107倍。
    所述的还原剂和水的物质的量比例变化范围为：1∶105-30∶1。
  10. 按照权利要求9所述一种溶液中稳定的贵金属孤原子材料的制备方法，其特征在于所述贵金属化合物前驱体包括：氯铂酸、氯铂酸钠、氯铂酸钾、氯化亚铂、氯化铂、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)二氯化铂或四氯铂酸铵中的一种。
  11. 按照权利要求9所述的一种溶液中稳定的贵金属孤原子材料的制备方法，其特征在于所述还原剂为醇类化合物、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。
  12. 按照权利要求11所述的一种溶液中稳定的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为甲醇、乙醇、丙醇、异丙醇、正丁醇，异丁醇，仲丁醇，叔丁醇、乙二醇，丙三醇中的一种或几种混合物。
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