RESUMO
Despite the fundamental and practical significance of the hydrogen evolution reaction (HER), the reaction kinetics at the molecular level are not well-understood, especially in basic media. Here, with ZIF-67-derived Co-based carbon frameworks (Co/NCs) as model catalysts, we systematically investigated the effects of different reaction parameters on the HER kinetics and discovered that the HER activity was directly dependent not on the type of nitrogen in the carbon framework but on the relative content of surface hydroxyl and water (OH-/H2O) adsorbed on Co active sites embedded in carbon frameworks. When the ratio of the OH-/H2O was close to 1:1, the Co/NC nanocatalyst showed the best reaction performance under the condition of high-pH electrolytes, e.g., an overpotential of only 232 mV at a current density of 10 mA cm-2 in the 1 M KOH electrolyte. We unambiguously identified that the structural water molecules (SWs) in the form of hydrous hydroxyl complexes absorbed on metal centers {OHad·H2O@M+} were catalytic active sites for the enhanced HER, where M+ could be transition or alkaline metal cations. Different from the traditional hydrogen bonding of water, the hydroxyl (hydroxide) groups and water molecules in the SWs were mainly bonded together via the spatial interaction between the p orbitals of O atoms, exhibiting features of a delocalized π-bond with a metastable state. These newly formed surface bonds or transitory states could be new weak interactions that synergistically promote both interfacial electron transfer and the activation of water (dissociation of O-H bonds) at the electrode surface, i.e., the formation of activated H adducts (H*). The capture of new surface states not only explains pH-, cation-, and transition-metal-dependent hydrogen evolution kinetics but also provides completely new insights into the understanding of other electrocatalytic reductions involving other small molecules, including CO2, CO, and N2.
RESUMO
On the origin of photoluminescence of noble metal NCs, there are always hot debates: metal-centered quantum-size confinement effect VS ligand-centered surface state mechanism. Herein, we provided solid evidence that structural water molecules (SWs) confined in the nanocavity formed by surface-protective-ligand packing on the metal NCs are the real luminescent emitters of Au-Ag bimetal NCs. The Ag cation mediated Au-Ag bimetal NCs exhibit the unique pH-dependent dual-emission characteristic with larger Stokes shift up to 200 nm, which could be used as potential ratiometric nanosensors for pH detection. Our results provide a completely new insight on the understanding of the origin of photoluminescence of metal NCs, which elucidates the abnormal PL emission phenomena, including solvent effect, pH-dependent behavior, surface ligand effect, multiple emitter centers, and large-Stoke's shift.
