Operando Spectroscopic Monitoring of Metal Chalcogenides for Overall Water Splitting: New Views of Active Species and Sites.

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.