6533b7d4fe1ef96bd12628dc

RESEARCH PRODUCT

Atomically Precise Alkynyl-Protected Metal Nanoclusters as a Model Catalyst: Observation of Promoting Effect of Surface Ligands on Catalysis by Metal Nanoparticles

Hai-feng SuShui-chao LinHannu HäkkinenNanfeng ZhengYu WangZichao TangZichao TangBoon K. TeoXian-kai WanLiting RenQuan-ming WangGang LiSami Malola

subject

Chemical substanceIntermetallic02 engineering and technology010402 general chemistry01 natural sciencesBiochemistrycatalystsCatalysisCatalysisNanoclustersMetalHydrolysisColloid and Surface ChemistryPolymer chemistryCluster (physics)Organic chemistryta116intermetallic nanoclustersta114ChemistryphenylalkynylGeneral Chemistry021001 nanoscience & nanotechnology0104 chemical sciencessurface ligandsvisual_artvisual_art.visual_art_medium0210 nano-technologyScience technology and society

description

Metal nanoclusters whose surface ligands are removable while keeping their metal framework structures intact are an ideal system for investigating the influence of surface ligands on catalysis of metal nanoparticles. We report in this work an intermetallic nanocluster containing 62 metal atoms, Au34Ag28(PhC≡C)34, and its use as a model catalyst to explore the importance of surface ligands in promoting catalysis. As revealed by single-crystal diffraction, the 62 metal atoms in the cluster are arranged as a four-concentric-shell Ag@Au17@Ag27@Au17 structure. All phenylalkynyl (PA) ligands are linearly coordinated to the surface Au atoms with staple "PhC≡C-Au-C≡CPh" motif. Compared with reported thiolated metal nanoclusters, the surface PA ligands on Au34Ag28(PhC≡C)34 are readily removed at relatively low temperatures, while the metal core remains intact. The clusters before and after removal of surface ligands are used as catalysts for the hydrolytic oxidation of organosilanes to silanols. It is, for the first time, demonstrated that the organic-capped metal nanoclusters work as active catalysts much better than those with surface ligands partially or completely removed.

https://doi.org/10.1021/jacs.5b12730