Operando bonding nickel thiolate with CdS as efficient photocatalyst for hydrogen evolution.

Area of Science:

• Materials Science
• Catalysis
• Photochemistry

Background:

• Semiconductor photocatalysts are vital for energy conversion.
• Metallic nanoclusters can enhance photocatalytic activity.
• Understanding nanocluster-cocatalyst interactions is key for optimizing performance.

Purpose of the Study:

• To synthesize nickel nanoclusters as cocatalysts for CdS.
• To investigate their role in enhancing photocatalytic hydrogen evolution.
• To elucidate the mechanism of cocatalyst activation and performance enhancement.

Main Methods:

• Synthesis of nickel thiolate nanoclusters (Ni 4(S-cy) 8).
• Fabrication of CdS photocatalysts loaded with nickel nanoclusters.
• Photocatalytic hydrogen evolution experiments under visible light irradiation.
• Analysis of nanocluster-semiconductor interactions and surface species.

Main Results:

• A 5 wt% loading of nickel nanoclusters on CdS achieved a hydrogen evolution rate of 106 mmol g cat -1 h -1.
• This performance is five times higher than that of pure CdS.
• Ligand removal and embedding of nickel species onto the CdS surface were observed, facilitated by Ni-S bonds.

Conclusions:

• Nickel nanoclusters, upon ligand removal, form active nickel species on CdS, significantly enhancing photocatalytic hydrogen evolution.
• The dynamic evolution of nanoclusters during catalysis is crucial for cocatalyst function.
• This study demonstrates the potential of using initially inert species to create highly efficient photocatalytic components.