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 ( Zr 6 , Zr 18 , and Zr 70 ) 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, Zr 6 and Zr 70 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 Zr 6 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.
Jing-Yu Sun,De-Sheng Wei,Bao-Xu Jiang,Xiaohong Li,Yu-Teng Zhang,Haihui Yu,Shuaibing Ma,Shuangbao Li
We present two bimetallic architectures cooperatively assembled from trinuclear zirconocene units (Cp3Zr3, Cp = η5-C5H5) and redox-active ferrocene-based ligands (ferrocene carboxylic acid (HFcA) or 1,1-ferrocene dicarboxylic acid (H2FcDA)). Interestingly, single-crystal analysis revealed that Cp3Zr3 units exhibited diverse coordination behaviors upon combination with ferrocene derivatives, ultimately leading to two heterometallic clusters: {Zr3Fc3} with a metallocavitand structure and {Zr12Fc4} with a molecular ring architecture. Notably, the incorporation of ferrocene units provides a photosensitizing center, enabling excellent photocatalytic Fenton-like degradation of methylene blue with efficiencies of 88.86% {Zr3Fc3} and 99.85% {Zr12Fc4}. Furthermore, the DFT calculation results suggest that the HOMO → LUMO transition mainly involves metal-to-core charge transfer (MCCT) from the iron center of the ferrocenyl groups to the Zr-oxo cluster core. This work not only advances the structural diversity of ferrocene-functionalized zirconium-oxo clusters but also offers valuable insights into high-performance Fenton-like photocatalysts.
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