Size Fractionation of Two‐Dimensional Sub‐Nanometer Thin Manganese Dioxide Crystals towards Superior Urea Electrocatalytic Conversion

Abstract

A universal technique has been proposed to sort two‐dimensional (2D) sub‐nanometer thin crystals (manganese dioxide MnO₂ and molybdenum disulfide MoS₂) according to their lateral dimensions. This technique is based on tuning the zeta potential of their aqueous dispersions which induces the selective sedimentation of large‐sized 2D crystals and leaves the small‐sized counterparts in suspension. The electrocatalytic properties of as‐obtained 2D ultrathin crystals are strongly dependent on their lateral size. As a proof‐of‐concept study, the small‐sized MnO₂ nanocrystals were tested as the electrocatalysts for the urea‐oxidation reaction (UOR), which showed outstanding performance in both half reaction and full electrolytic cell. A mechanism study reveals the enhanced performance is associated with the remarkable structural properties of MnO₂ including ultrathin (ca. 0.95 nm), laterally small‐sized (50–200 nm), and highly exposed active centers.