Construction of Pt Single-Atom and Cluster/FeOOH Synergistic Active Sites for Efficient Electrocatalytic Hydrogen Evolution Reaction

The design of efficient catalysts that synergistically promote *H2O decomposition, H-2 formation, and desorption is critical to accelerate hydrogen evolution reaction (HER) kinetics but remains a significant challenge. Herein, we design an efficient catalyst of Pt/FeOOH@NiFe LDHs with Pt single-atom and cluster distribution induced by amorphous FeOOH. The Pt/FeOOH@NiFe LDHs with a low Pt content of 2 wt % exhibit ultralow HER overpotentials of 20 and 85 mV in alkaline media (5 and 40 mV in acidic media) to achieve the current densities of 10 and 100 mA cm(-2). The overpotentials of specific activity normalized by the electrochemically active surfaces (ECSA) are 100 mV@0.2 mA cm(ECSA)(-2) and 140 mV@0.4 mA cm(ECSA)(-2). The Tafel slope is 51 mV dec(-1), and the HER process follows the Volmer-Hyrovsky mechanism. Moreover, the overall water splitting requires only low voltages of 1.46 V@10 mA cm(-2) and 1.61 V@100 mA cm(-2), which are better than most reported catalysts. Experimental and theoretical studies show that the amorphous FeOOH can induce the formation of Pt single-atom and cluster with electron redistribution, and the formed Pt single-atom and cluster/FeOOH synergistic active sites exhibit superior HER performance. The amorphous FeOOH in Pt/FeOOH@NiFe LDHs facilitates the adsorption and activation of H2O, and the Pt single-atom and cluster play a key role in the formation and desorption of H-2, synergistically accelerating the HER kinetics.