Volcano-type relationship between oxidation states and catalytic activity of single-atom catalysts towards hydrogen evolution
Dong Cao, Haoxiang Xu, Hongliang Li, Chen Feng, Jie Zeng, Daojian Cheng
Abstract
Abstract To date, the effect of oxidation state on activity remains controversial in whether higher or lower oxidation states benefit the enhancement of catalytic activity. Herein, we discover a volcanic relationship between oxidation state and hydrogen evolution reaction activity based on Os single-atom catalysts. Firstly, a series of Os SACs with oxidation states ranging from + 0.9 to + 2.9 are synthesized via modifying the coordination environments, including Os-N 3 S 1 , Os-N 4 , Os-S 6 , Os-C 3 , and Os-C 4 S 2 . A volcano-type relation between oxidation states and hydrogen evolution activity emerge with a summit at a moderate experimental oxidation state of + 1.3 (Os-N 3 S 1 ). Mechanism studies illustrate that with increasing oxidation states, the adsorption of H atoms on Os is strengthened due to increased energy level and decreased occupancy of anti-bonding states of Os-H bond until the anti-bonding states become empty. Further increasing the oxidation states weakens hydrogen adsorption because of the decreased occupancy of Os-H bonding states. In this work, we emphasize the essential role of oxidation state in manipulating activity, which offers insightful guidance for the rational design of single-atom catalysts.