ABSTRACT
Designing efficient and robust oxygen evolution reaction (OER) electrocatalysts is of great importance for various electrochemical energy storage and conversion applications. Herein, we developed IrP2nanocrystals uniformly anchored in P,N-codoped carbon nanosheets (IrP2@PNC-NS) as highly active OER electrocatalysts. The ultrathin PNC-NS reconstructs an agaric-like porous structure, which can inhibit the agglomeration of the IrP2nanocrystals effectively. Moreover, thein-situphosphatization leads to the formation of a strong electron interaction between PNC-NS and IrP2nanocrystals, endowing the heterostructure materials with satisfying synergistic effects. Benefiting from the collaborative advantages of ideal configuration structure and favorable synergistic effects, IrP2@PNC-NS exhibits excellent OER performance with a low overpotential of 221 mV at 10 mA cm-2, and a small Tafel slope of 37.5 mV dec-1. DFT calculations reveal that the synergistic effects derived from the IrP2/PNC interfaces, which can effectively tune the activation barriers towards facilitating the oxygen evolution process. This work provides new insight into the design of heterostructure materials for advanced OER electrocatalysts.
ABSTRACT
The electrochemical N2 reduction reaction (NRR) is emerging as a promising alternative to the industrial Haber-Bosch process for distributed and modular production of NH3 . Nevertheless, developing high-efficiency catalysts to simultaneously realize both high activity and selectivity for the development of a sustainable NRR is very critical but extremely challenging. Here, a unique plasma-assisted strategy is developed to synthesize iridium diphosphide nanocrystals with abundant surface step atoms anchored in P,N-codoped porous carbon nanofilms (IrP2 @PNPC-NF), where the edges of the IrP2 nanocrystals are extremely irregular, and the ultrathin PNPC-NF possesses a honeycomb-like macroporous structure. These characteristics ensure that IrP2 @PNPC-NF delivers superior NRR performance with an NH3 yield rate of 94.0 µg h-1 mg-1 cat. and a faradaic efficiency (FE) of 17.8%. Density functional theory calculations reveal that the unique NRR performance originates from the low-coordinate step atoms on the edges of IrP2 nanocrystals, which can lower the reaction barrier to improve the NRR activity and simultaneously inhibit hydrogen evolution to achieve a high FE for NH3 formation. More importantly, such a plasma-assisted strategy is general and can be extended to the synthesis of other high-melting-point noble-metal phosphides (OsP2 @PNPC-NF, Re3 P4 @PNPC-NF, etc.) with abundant step atoms at lower temperatures.
