Peculiar reactions between interstitial compounds of transition metals and hydrogen peroxide and characterization of resultant materials

过渡金属间隙化合物与过氧化氢之间的特殊反应及所得材料的表征

基本信息

  • 批准号:
    09450315
  • 负责人:
  • 金额:
    $ 10.05万
  • 依托单位:
  • 依托单位国家:
    日本
  • 项目类别:
    Grant-in-Aid for Scientific Research (B).
  • 财政年份:
    1997
  • 资助国家:
    日本
  • 起止时间:
    1997 至 2000
  • 项目状态:
    已结题

项目摘要

It has been found that some tungsten oxide clusters like peroxo-oxalato-polytungstate formed by a reaction of tungsten carbide with hydrogen peroxide show high proton conductivity. In this fiscal year have studied a methodology to incorporate such a cluster into an organic matrix to enhance chemical stability, and evaluated nanohybrid materials thus obtained as a proton conductive solid electrolyte membrane.We obtained a homogeneous solution of a peroxotungstate complex by reacting tungsten trioxide monohydrate with hydrogen peroxide at 40℃ for 24 h. A carboxylic acid such as oxalic, malonic or dimethylmalonic acid was added to the solution at the ratio of 0.25-4.0 to tungsten atom, to yield a chelated complex. This solution was added to a methanol solution of alchoxysillilated poly (ethyleneoxide)-600 and polymerized at 60℃ by a sol-gel process. A homogeneous and transparent membrane was formed.Proton conductivity of those membranes was measured in the temperature range of 25-160℃ under suturated water vapor pressure by the ac impedance method. Conductivity of a typical membrane at 80℃ was 1.4x10^<-2> Scm-1, which was 10 times higher that that of a composite membrane fabricated by simply blending PEO and tungsten trioxide dihydrate as an inorganic high proton conductor. This means that tungstate clusters dispersed at a nano-level homogeneity throughout the PEO-matrix form a percolation path for fast proton transport. Such a situation was also confirmed by vibration spectra and X-ray diffraction. Although conductivity fell with raising temperature above 100℃, it remained at a level of 10^<-4> Scm^<-1> in the range of 140-160℃. Bulky ligands such as dimethylmalonate tended to suppress conductivity fall at high temperature.
研究发现碳化钨与过氧化氢反应形成的过氧化物-草酸盐-多钨酸钨团簇具有较高的质子导电性。在本财政年度,我们研究了一种方法,将这种簇结合到有机基质中,以提高化学稳定性,并评估了由此获得的作为质子导电固体电解质膜的纳米杂化材料。将一水三氧化钨与双氧水在40℃下反应24 h,得到过氧化物钨酸配合物的均匀溶液。在溶液中加入草酸、丙二酸或二甲基丙二酸等羧酸,其与钨原子的比例为0.25-4.0,得到络合物。将该溶液加入到醇烷基化聚环氧乙烷-600的甲醇溶液中,在60℃下采用溶胶-凝胶法进行聚合。形成均匀透明的膜。在饱和水蒸汽压下,用交流阻抗法测定了这些膜在25 ~ 160℃温度范围内的质子电导率。典型膜在80℃时的电导率为1.4 × 10^<-2> sc -1,是单纯将PEO与二水合三氧化钨作为无机高质子导体混合制备的复合膜的10倍。这意味着钨酸盐团簇以纳米级均匀性分散在peo -基质中,形成了快速质子传输的渗透路径。振动谱和x射线衍射也证实了这种情况。虽然电导率在100℃以上随温度升高而下降,但在140 ~ 160℃范围内保持在10^<-4> Scm^<-1>的水平。体积大的配体如二甲基丙二酸盐倾向于抑制高温下的电导率下降。

项目成果

期刊论文数量(28)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
H.Nakajima, et al: "Reaction of tungsten metal powder with hydrogen peroxide to form peroxo tungstates,an useful precursor of proton conductor" Chemistry Letters. 693-694 (1997)
H.Nakajima 等人:“钨金属粉末与过氧化氢反应形成过氧钨酸盐,一种有用的质子导体前体”《化学快报》。
  • DOI:
  • 发表时间:
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  • 影响因子:
    0
  • 作者:
  • 通讯作者:
Y.Tanaka, et.al: "Proton Conductivity of Tungsten Trioxide Hydrates"Seisan-Kenkyu. 52. 523-527 (2000)
Y.Tanaka 等人:“三氧化钨水合物的质子传导率”Seisan-Kenkyu。
  • DOI:
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    0
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日比野光宏ら: "W及びMo系層状酸化物水和物のプロトン伝導性"電気化学会第67回大会学術講演要旨集. (2000)
Mitsuhiro Hibino 等人:“W 和 Mo 基层状氧化物水合物的质子传导性”电化学学会第 67 届年会论文集(2000 年)。
  • DOI:
  • 发表时间:
  • 期刊:
  • 影响因子:
    0
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  • 通讯作者:
Y.M.LI, et.al: "Proton Conductivity of Tungsten Trioxide Hydrates at Intermediate Temperature"Solid State Ionics. 134. 271-279 (2000)
Y.M.LI 等人:“中温三氧化钨水合物的质子电导率”固态离子学。
  • DOI:
  • 发表时间:
  • 期刊:
  • 影响因子:
    0
  • 作者:
  • 通讯作者:
T.Kudo: "Proton Conductivity of Tungsten Trioxide Hydrates at Intermediate Temperature"The 7^<th> Asian Conference on Solid State Ionics. (2000)
T.Kudo:“中温三氧化钨水合物的质子电导率”第七届亚洲固态离子学会议。
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    0
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KUDO Tetsuichi其他文献

KUDO Tetsuichi的其他文献

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{{ truncateString('KUDO Tetsuichi', 18)}}的其他基金

Development of Bicontinuous Mesoporous Oxide Materials
双连续介孔氧化物材料的研制
  • 批准号:
    15360348
  • 财政年份:
    2003
  • 资助金额:
    $ 10.05万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
Lithium intercalation properties of V205-based thin films and their application to thin film batteries
V2O5基薄膜的嵌锂性能及其在薄膜电池中的应用
  • 批准号:
    10555299
  • 财政年份:
    1998
  • 资助金额:
    $ 10.05万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
Metal to insulator transition of VO2-based thin films prepared by a coating method and its application to smart windows
涂覆法制备VO2基薄膜的金属-绝缘体转变及其在智能窗中的应用
  • 批准号:
    08555213
  • 财政年份:
    1996
  • 资助金额:
    $ 10.05万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
Study of Correlation between Ionic Transport and the Structure of Solids
离子输运与固体结构的相关性研究
  • 批准号:
    07239102
  • 财政年份:
    1995
  • 资助金额:
    $ 10.05万
  • 项目类别:
    Grant-in-Aid for Scientific Research on Priority Areas
Low Temperature Synthesis of Metal Oxide Bronze Phases and their Electric Properties
金属氧化物青铜相的低温合成及其电性能
  • 批准号:
    06453118
  • 财政年份:
    1994
  • 资助金额:
    $ 10.05万
  • 项目类别:
    Grant-in-Aid for General Scientific Research (B)
Electrochromism of mixed polyacid films and its application for a smart window
混合多元酸薄膜的电致变色及其在智能窗中的应用
  • 批准号:
    04555182
  • 财政年份:
    1992
  • 资助金额:
    $ 10.05万
  • 项目类别:
    Grant-in-Aid for Developmental Scientific Research (B)

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    2024
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    2023
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  • 批准号:
    23K15992
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    2023
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    10553870
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