Enhancement of Aqua‐Ammonia Vapor on Proton Conduction for Two Water‐Tolerant Complicated Copper Cluster Compounds

Abstract

Abstract By adopting two similar acyl thiourea‐based carboxylate ligands, 2‐(3‐benzoylthioureido)propionic acid (H 3 BTPA) and 2‐(3‐benzoylthioureido)ethanoic acid (H 3 BTEA) to react with Cu(OAc) 2 , respectively, one 2D cluster polymer [Cu I 6 Cu II 6 (BTPA) 6 (H 2 O) 10 ] n ( 1 ) and one 0D cluster [Cu I 6 Cu II 6 (BTEA) 6 (H 2 O) 10 (DMF) 2 ]⋅6H 2 O ( 2 ) (DMF= N , N ‐dimethylformamide) were successfully prepared and structurally characterized. The optimized proton conductivity for 1 is 1.16 × 10 −5 S⋅cm −1 under 98% RH and 100 °C, which can be increased to a higher value of 7.70 × 10 −4 S⋅cm −1 under aqua‐ammonia vapor from 2.0 M of NH 3 ⋅H 2 O solution. For 2 , the largest proton conductivity of 9.80 × 10 −4 S⋅cm −1 could be obtained under aqua‐ammonia vapor. Through PXRD determinations, water and ammonia adsorption measurements, E a calculations, a clear understanding of their proton conduction mechanisms as well as the enhancement of aqua‐ammonia vapor on the proton conduction has been obtained.