Customizing a Hyperbranched Ligand Confers Supported Platinum Nanoclusters with Unexpected Catalytic Activity toward
Jingyun Ye1, Chenhui Li1, Xiaoqiu Yao1
1Department of Polymer Materials, School of Materials Science and Engineering, Tongji University, 4800 Cao-an Road, Shanghai 201804, China.
Abstract:
We here show that a dendritic molecule combined with ligand merit confers supported platinum nanoclusters (PtNCs) with unprecedented catalytic performance. Branched polyethylenimine (PEI, Mn = 2000 D) patched on a porous bead is modified with 2-(diphenylphosphino)benzaldehyde (dppb) before being used to mediate a platinum nanoparticle/nanocluster (Pt0). The catalytic activity of Pt0 toward the reduction of 4-nitrophenol (4-NP) is evaluated from the parameter of Pt-normalized rate constant (kc). Optimization of the dppb level along with transformation of the PEI hydrogens into diol or trimethylammonium groups imparts supported Pt0 unprecedented activity (kc = 19.2 L mmol-1 s-1 and turnover frequency (TOF) = 1041 h-1). The supported Pt0 at an extremely low dosage of 0.1 ppm promotes 98% conversion of 4-NP within minutes and is well recyclable. The striking catalytic activity is attributed to the combination of orthogonal ligand properties such as weak ligand nature, catalyst-activating ability, excellent substrate affinity, and effect on PtNC-size mediation of the ligand.
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