<i>Operando</i> Spectroscopic Monitoring of Metal Chalcogenides for Overall Water Splitting: New Views of Active Species and Sites
Yonggui Zhao, Wenchao Wan, Rolf Erni, Long Pan, Greta R. Patzke
Abstract
Abstract Metal‐based chalcogenides exhibit great promise for overall water splitting, yet their intrinsic catalytic reaction mechanisms remain to be fully understood. In this work, we employed operando X‐ray absorption (XAS) and in situ Raman spectroscopy to elucidate the structure–activity relationships of low‐crystalline cobalt sulfide (L−CoS) catalysts toward overall water splitting. The operando results for L−CoS catalyzing the alkaline hydrogen evolution reaction (HER) demonstrate that the cobalt centers in the bulk are predominantly coordinated by sulfur atoms, which undergo a kinetic structural rearrangement to generate metallic cobalt in S−Co−Co−S moieties as the true catalytically active species. In comparison, during the acidic HER, L−CoS undergoes local structural optimization of Co centers, and H 2 production proceeds with adsorption/desorption of key intermediates atop the Co−S−Co configurations. Further operando characterizations highlight the crucial formation of high‐valent Co 4+ species in L−CoS for the alkaline oxygen evolution reaction (OER), and the formation of such active species was found to be far more facile than in crystalline Co 3 O 4 and Co‐LDH references. These insights offer a clear picture of the complexity of active species and site formation in different media, and demonstrate how their restructuring influences the catalytic activity.