title: Atomically Precise Alkynyl-Protected Metal Nanoclusters as a Model Catalyst: Observation of Promoting Effect of Surface Ligands on Catalysis by Metal Nanoparticles.
abstract: 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.
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University , Xiamen 361005, China.
authors.forename: Yu
authors.initials: Y
authors.lastname: Wang
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University , Xiamen 361005, China.
authors.forename: Xian-Kai
authors.initials: XK
authors.lastname: Wan
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University , Xiamen 361005, China.
authors.forename: Liting
authors.initials: L
authors.lastname: Ren
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University , Xiamen 361005, China.
authors.forename: Haifeng
authors.initials: H
authors.lastname: Su
authors.affiliation: State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences , Dalian 116023, China.
authors.forename: Gang
authors.initials: G
authors.lastname: Li
authors.affiliation: Departments of Physics and Chemistry, Nanoscience Center, University of Jyväskylä , Jyväskylä FI-40014 Finland.
authors.forename: Sami
authors.initials: S
authors.lastname: Malola
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University , Xiamen 361005, China.
authors.forename: Shuichao
authors.initials: S
authors.lastname: Lin
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University , Xiamen 361005, China.|State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences , Dalian 116023, China.
authors.forename: Zichao
authors.initials: Z
authors.lastname: Tang
authors.affiliation: Departments of Physics and Chemistry, Nanoscience Center, University of Jyväskylä , Jyväskylä FI-40014 Finland.
authors.forename: Hannu
authors.initials: H
authors.lastname: Häkkinen
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University , Xiamen 361005, China.
authors.forename: Boon K
authors.initials: BK
authors.lastname: Teo
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University , Xiamen 361005, China.
authors.forename: Quan-Ming
authors.initials: QM
authors.lastname: Wang
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University , Xiamen 361005, China.
authors.forename: Nanfeng
authors.initials: N
authors.lastname: Zheng