Blurring the boundary between homogenous and heterogeneous catalysis using palladium nanoclusters with dynamic surfaces
Artikel i vetenskaplig tidskrift, 2021

Using a magnetron sputtering approach that allows size-controlled formation of nanoclusters, we have created palladium nanoclusters that combine the features of both heterogeneous and homogeneous catalysts. Here we report the atomic structures and electronic environments of a series of metal nanoclusters in ionic liquids at different stages of formation, leading to the discovery of Pd nanoclusters with a core of ca. 2 nm surrounded by a diffuse dynamic shell of atoms in [C4C1Im][NTf2]. Comparison of the catalytic activity of Pd nanoclusters in alkene cyclopropanation reveals that the atomically dynamic surface is critically important, increasing the activity by a factor of ca. 2 when compared to compact nanoclusters of similar size. Catalyst poisoning tests using mercury and dibenzo[a,e]cyclooctene show that dynamic Pd nanoclusters maintain their catalytic activity, which demonstrate their combined features of homogeneous and heterogeneous catalysts within the same material. Additionally, kinetic studies of cyclopropanation of alkenes mediated by the dynamic Pd nanoclusters reveal an observed catalyst order of 1, underpinning the pseudo-homogeneous character of the dynamic Pd nanoclusters.

Författare

Israel Cano

University of Nottingham

Andreas Weilhard

University of Nottingham

Carmen Martin

University of Nottingham

Jose Pinto

University of Nottingham

Rhys W. Lodge

University of Nottingham

Ana R. Santos

University of Nottingham

Graham A. Rance

University of Nottingham

Elina Harriet Åhlgren

University of Nottingham

Erlendur Jonsson

Chalmers, Fysik, Materialfysik

University of Cambridge

Jun Yuan

University of York

Z. Y. Li

University of Birmingham

Peter Licence

University of Nottingham

Andrei N. Khlobystov

University of Nottingham

Jesum Alves Fernandes

University of Nottingham

Nature Communications

2041-1723 (ISSN)

Vol. 12 1 4965

Ämneskategorier

Oorganisk kemi

Fysikalisk kemi

Organisk kemi

DOI

10.1038/s41467-021-25263-6

Mer information

Senast uppdaterat

2021-09-13