LAUSR

Single‐atom catalysts (SACs), on account of their outstanding catalytic potential, are currently emerging as high‐performance materials in the field of heterogeneous catalysis. Constructing a strong interaction between the single atom and its supporting matrix plays a pivotal role. Herein, Ti3C2Tx‐MXene‐supported Ni SACs are reported by using a self‐reduction strategy via the assistance of rich Ti vacancies on the Ti3C2Tx MXene surface, which act as the trap and anchor sites for individual Ni atoms. The constructed Ni SACs supported by the Ti3C2Tx MXene (Ni SACs/Ti3C2Tx ) show an ultralow onset potential of −0.03 V (vs reversible hydrogen electrode (RHE)) and an exceptional operational stability toward the hydrazine oxidation reaction (HzOR). Density functional theory calculations suggest a strong coupling of the Ni single atoms and their surrounding C atoms, which optimizes the electronic density of states, increasing the adsorption energy and decreasing the reaction activation energy, thus boosting the electrochemical activity. The results presented here will encourage a wider pursuit of 2D‐materials‐supported SACs designed by a vacancy‐trapping strategy.