Atomic-Precise Active Site Surgery on Carboranylthiolate-Protected Silver Nanocluster Catalysts

Area of Science:

• Materials Science
• Nanotechnology
• Catalysis

Background:

• Precisely controlling metal nanocluster composition and structure is crucial for tailoring properties.
• Synthesizing nanoclusters with unsaturated coordination environments and active sites for enhanced catalysis remains challenging.

Purpose of the Study:

• To develop an atomic-level strategy for creating and manipulating active metal sites on metal nanoclusters.
• To investigate the catalytic performance of nanoclusters with exposed metal sites in electrocatalytic nitrate reduction.

Main Methods:

• Construction of a novel Ag13 icosahedral nanocluster (AgP) stabilized by carboranethiolate and phosphine ligands.
• Solvent-regulated transformation of AgP into Ag nanoclusters with exposed silver atoms.
• Site-specific heterometal (Cu) substitution to create Cu-doped Ag nanoclusters (AgCu).

Main Results:

• Ag and AgCu nanoclusters with exposed metal sites exhibited improved catalytic activity in electrocatalytic nitrate reduction reaction (NO3RR) compared to AgP.
• AgCu demonstrated superior performance, achieving a high faradaic efficiency (FE) of 90.4% for NH3 production and a total FE of 99.6%.
• The study successfully generated and manipulated open metal sites on metal nanoclusters.

Conclusions:

• The proposed atomic-level surgical strategy provides a pathway for generating and manipulating open metal sites on metal nanoclusters.
• This approach offers new perspectives for designing and synthesizing efficient metal nanocluster-based catalytic materials.
• Exposed metal sites significantly enhance catalytic activity, particularly for nitrate reduction to ammonia.