Electronegativity-Induced Charge Balancing to Boost Stability and Activity of Amorphous Electrocatalysts (vol 34, 2100537, 2022)

Amorphization is an efficient strategy to activate intrinsically inert catalysts. However, the low crystallinity of amorphous catalysts often causes high solubility and poor electrochemical stability in aqueous solution. Here, a different mechanism is developed to simultaneously stabilize and activate the water-soluble amorphous MoSxOy via a charge-balancing strategy, which is induced by different electronegativity between the co-dopants Rh (2.28) and Sn (1.96). The electron-rich Sn prefers to stabilize the unstable apical O sites in MoSxOy through charge transfer, which can prevent the H from attacking. Meanwhile, the Rh, as the charge regulator, shifts the main active sites on the basal plane from inert Sn to active apical Rh sites. As a result, the amorphous RhSn-MoSxOy exhibits drastic enhancement in electrochemical stability (eta(10) increases only by 12 mV) after 1000 cycles and a distinct activity (eta(10): 26 mV and Tafel: 30.8 mV dec(-1)) for the hydrogen evolution reaction in acidic solution. This work paves a route for turning impracticably water-soluble catalysts into treasure and inspires new ideas to design high-performance amorphous electrocatalysts.