Carbon Nitride Loaded with an Ultrafine, Monodisperse, Metallic Platinum‐Cluster Cocatalyst for the Photocatalytic Hydrogen‐Evolution Reaction

Abstract

For the realization of a next‐generation energy society, further improvement in the activity of water‐splitting photocatalysts is essential. Platinum (Pt) is predicted to be the most effective cocatalyst for hydrogen evolution from water. However, when the number of active sites is increased by decreasing the particle size, the Pt cocatalyst is easily oxidized and thereby loses its activity. In this study, a method to load ultrafine, monodisperse, metallic Pt nanoclusters (NCs) on graphitic carbon nitride is developed, which is a promising visible‐light‐driven photocatalyst. In this photocatalyst, a part of the surface of the Pt NCs is protected by sulfur atoms, preventing oxidation. Consequently, the hydrogen‐evolution activity per loading weight of Pt cocatalyst is significantly improved, 53 times, compared with that of a Pt‐cocatalyst loaded photocatalyst by the conventional method. The developed method is also effective to enhance the overall water‐splitting activity of other advanced photocatalysts such as SrTiO3 and BaLa4Ti4O15.

Fluorinated carbon encapsulated NiO cluster/TiO2 nanotubes as a robust photocatalyst for hydrogen evolution

“…21-1272). 17,19 The absence of diffraction peaks for NiO suggests that the NiO clusters are small in size and are highly dispersed. 19 Peak shifts due to doping of the Ni into the TiO 2 were also not observed, confirming that the NiO present is anchored at the surface.…”

“…13–16 The particle size of the cocatalyst significantly impacts the specific surface area, electronic structure and the number of surface active sites. 17,18 It also effectively changes the energy level and the work function alignment at the catalyst/cocatalyst interface, and greatly impacts the surface binding property of the composite. This is especially the case when the particle size drops below ca.…”

Nitrogen defects and porous self-supporting structure carbon nitride for visible light hydrogen evolution

“…The holes on the CB are consumed by the sacrificial agent triethanolamine, and the photogenerated electrons are transferred to the Pt supported on the catalyst surface, and then undergo a reduction reaction with H + to generate H 2 . 52 Meanwhile, the self-supporting multi-channel structure enhances the scattering of incident light, thereby improving the utilization of visible light. The thin-walled structure greatly shortens the transport path of photogenerated carriers and accelerates the transport rate of electrons from the interior to the surface.…”

Elucidation of the electronic structures of thiolate-protected gold nanoclusters by electrochemical measurements

“…However, it is desirable to clarify the electronic states of Au n (SR) m NCs on catalyst supports when considering their use in catalytic reactions in the gas or solid phase. 135,147–151 In this case, it is expected that the electronic/geometric state of Au n (SR) m NCs will also significantly change during catalytic reaction. For instance, ligands have also been reported to desorb from Au n (SR) m NCs upon applying potential 152 and the catalytic properties to be depends on the electronic state of Au n (SR) m NCs.…”