Breaking the Sabatier Principle by Dynamic Adsorption-Desorption Decoupling in Electrocatalytic Hydrogen Evolution

Abstract

The Sabatier principle establishes a fundamental trade-off in heterogeneous electrocatalysis.In the hydrogen evolution reaction (HER), this trade-off is manifested by the coupling of Volmer step, which requires strong hydrogen adsorption, with the Heyrovsky/Tafel step, which favors facile desorption, thus giving rise to the classical volcano relationship and limiting activity even at $\hat{I}”G=0$. Here, we demonstrate a ferroelectric platform with dynamic tunability -- monolayer GeS${}_2$ decorated with transition metal atoms as a proof-of-concept -- where polarization-driven surface electronic reconstruction enables real-time modulation of intermediate binding strength, thereby breaking the Sabatier constraint. Reversible control of hydrogen adsorption allows strong H binding to accelerate the Volmer step, followed by weakened adsorption to promote the Heyrovsky/Tafel step.This dynamic adsorption-desorption decoupling not only surpasses the volcano limit to achieve unprecedented HER activity, but also establishes a general paradigm for designing adaptive electrocatalysts capable of reconfiguring under operating conditions.

9 pages, 5 figures