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Keeping Superprotonic Conductivity over a Wide Temperature Region via Sulfate Hopping Sites‐Decorated Zirconium‐Oxo Clusters
Ist Teil von
Small (Weinheim an der Bergstrasse, Germany), 2022-12, Vol.18 (48), p.e2205444-n/a
Ort / Verlag
Weinheim: Wiley Subscription Services, Inc
Erscheinungsjahr
2022
Link zum Volltext
Quelle
Wiley Blackwell Single Titles
Beschreibungen/Notizen
Metal‐oxo clusters have emerged as advanced proton conductors with well‐defined and tunable structures. Nevertheless, the exploitation of metal‐oxo clusters with high and stable proton conductivity over a relatively wide temperature range still remains a great challenge. Herein, three sulfate groups decorated zirconium‐oxo clusters (Zr6, Zr18, and Zr70) as proton conductors are reported, which exhibit ultrahigh bulk proton conductivities of 1.71 × 10−1, 2.01 × 10−2, and 3.73 × 10−2 S cm−1 under 70 °C and 98% relative humidity (RH), respectively. Remarkably, Zr6 and Zr70 with multiple sulfate groups as proton hopping sites show ultralow activation energies of 0.22 and 0.18 eV, respectively, and stable bulk conductivities of >10−2 S cm−1 between 30 and 70 °C at 98% RH. Moreover, a time‐dependent proton conductivity test reveals that the best performing Zr6 can maintain high proton conductivity up to 15 h with negligible loss at 70 °C and 98% RH, representing one of the best crystalline cluster‐based proton conducting materials.
Three zirconium‐oxo clusters decorated by sulfate groups, named Zr6, Zr18 and Zr70 are developed as proton conductors with superprotonic conductivities. Zr6 and Zr70 have stable proton conductivities of > 10−2 S cm−1 with ultralow activation energies between 30 and 70 °C, which is the first observed among metal‐oxo cluster‐based proton conductors reported thus far.