期刊
ACS APPLIED MATERIALS & INTERFACES
卷 13, 期 16, 页码 19138-19147出版社
AMER CHEMICAL SOC
DOI: 10.1021/acsami.1c01752
关键词
polyoxometalates; lanthanides; polymers; hydrogen bonds; proton transport
资金
- JSPS KAKENHI [JP18H02058, 20H02750]
- JSPS Core-to-Core program
- International Network on Polyoxometalate Science at Hiroshima University
- Grants-in-Aid for Scientific Research [20H02750] Funding Source: KAKEN
A novel hybrid material composed of a Preyssler-type polyoxometalate functionalized with a 9-coordinate Eu3+ and poly(allylamine) has been synthesized, exhibiting ultrahigh proton conductivity and robust crystalline structure. The approach of strengthening and extending hydrogen-bonding network enables the material to maintain high conductivity even under lower humidity conditions.
The exploration of composition-structure-function relationship in proton-conducting solids remains a challenge in materials chemistry. Polyoxometalate-based compounds have been long considered as candidates for proton conductors; however, their low structural stability and a large decrease in conductivity under reduced relative humidity (RH) have limited their applications. To overcome such limitations, the hybridization of polyoxometalates with proton-conducting polymers has emerged as a promising method. Besides, 4f lanthanide ions possess a high coordination number, which can be utilized to attract water molecules and to build robust frameworks. Herein, a Preyssler-type polyoxometalate functionalized with a 9-coordinate Eu3+ (Eu-[P5W30O110K](11-)) is newly synthesized and combined with poly(allylamine) with amine moieties as protonation sites. The resulting robust crystalline composite exhibits an ultrahigh proton conductivity >10(-2) S cm(-1) at 368 K and 90% RH, which is still >10(-3) S cm(-1) at 50% RH, due to the strengthened and extended hydrogen-bonding network.
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