Keeping Superprotonic Conductivity over a Wide Temperature Region via Sulfate Hopping Sites‐Decorated Zirconium‐Oxo Clusters

Abstract 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.