On the photocatalysis evolution of heteroatom-doped AgM nanoclusters.

Atomically precise metal nanoclusters doped with one or more heteroatom of other metals have exhibited extraordinary catalytic properties. Here we report a series of thiolate-protected AgM (M is dopant Ni, Pd and Pt) nanoclusters that adopt a similar structural framework like a distorted hexahedron, in which four Ag atoms are located at the midpoints of four side edges and two metal heteroatoms reside on the centres of the top and the bottom planes. The opposite orders of the catalytic performances of the three catalysts for the photocatalytic degradation of the methyl orange and rhodamine B dyes are found, which is attributed to two different types of inter-molecular recombination mechanisms.

Cd-driven surface reconstruction and photodynamics in gold nanoclusters.

With atomically precise gold nanoclusters acting as a starting unit, substituting one or more gold atoms of the nanocluster with other metals has become an effective strategy to create metal synergy for improving catalytic performances and other properties. However, so far detailed insight into how to design the gold-based nanoclusters to optimize the synergy is still lacking, as atomic-level exchange between the surface-gold (or core-gold) and the incoming heteroatoms is quite challenging without changing other parts. Here we report a Cd-driven reconstruction of Au(DMBT) (DMBT = 3,5-dimethylbenzenethiol), in which four Au(DMBT) staples are precisely replaced by two AuCd(DMBT) staples to form AuCd(DMBT) with the face-centered cubic inner core retained.

Ligand-protected AuRu and AuRu nanoclusters: distinct structures and implications for site-cooperation catalysis.

We report two ligand-protected AuRu and AuRu nanoclusters with distinct atomic-packing modes and electronic structures, both of which act as ideal model catalysts for identifying the catalytically active sites of catalysts on the nanoclusters. AuRu exhibits superior catalytic performances to AuRu for N-methylation of N-methylaniline to N-methylformanili, which is likely due to the site-cooperation catalysis of AuRu.

Precisely modulating the surface sites on atomically monodispersed gold-based nanoclusters for controlling their catalytic performances.

Atomically precise gold nanoclusters protected by ligands are being intensely investigated in current catalysis science, due to the definitive correlation between the catalytic properties and structures at an atomic level. By solving the crystal structures of the nanoclusters, coupled with in situ and ex situ spectroscopy, a very fundamental understanding can be achieved to learn what controls the catalytic activation, active site structure, and catalytic mechanism. Herein, we mainly focus on the recent progress in catalysis controlled by precisely modulating the surface structures of the nanoclusters, including the alteration of the surface motifs, the doping of heterogeneous atoms in the surface of the nanoclusters, and the surface ligand engineering.

Reactivity and Lability Modulated by a Valence Electron Moving in and out of 25-Atom Gold Nanoclusters.

The emergence of atomically precise metal nanoclusters with unique electronic structures provides access to currently inaccessible catalytic challenges at the single-electron level. We investigate the catalytic behavior of gold Au (SR) nanoclusters by monitoring an incoming and outgoing free valence electron of Au 6s . Distinct performances are revealed: Au (SR) is generated upon donation of an electron to neutral Au (SR) and this is associated with a loss in reactivity, whereas Au (SR) is generated from dislodgment of an electron from neutral Au (SR) with a loss in stability.

Ag Au (PET) Nanocluster: Dimeric Assembly of Au (PET) Enabled by Silver Atoms.

The assembly of atomically precise metal nanoclusters offers exciting opportunities to gain fundamental insights into the hierarchical assembly of nanoparticles. However, it is still challenging to control the assembly of individual nanoclusters at a molecular or atomic level. Herein, we report the dimeric assembly of Au (PET) (PET=2-phenylethanethiol), where two Au (PET) monomers are bridged together by two Ag atoms to form the Ag Au (PET) dimer.

The on-and-off dynamics of thiophene on a nickel cluster enables efficient hydrodesulfurization and excellent stability at high temperatures.

Despite significant advances in the synthesis and structural determination of atomically precise metal clusters, few studies have explored their catalytic applications in industrially important reactions. Here, we report a thiolate-stabilized Ni cluster for the efficient hydrodesulfurization of thiophene under relatively harsh reaction conditions while maintaining its atomic structure, which was enabled by the on-and-off dynamic state of thiophene on the cluster. Through a combined experimental and theoretical approach, we elucidate the activated structure and the catalytic mechanism.