Blurring the boundary between homogenous and heterogeneous catalysis using palladium nanoclusters with dynamic surfaces

Author:

Cano Israel,Weilhard Andreas,Martin CarmenORCID,Pinto Jose,Lodge Rhys W.,Santos Ana R.ORCID,Rance Graham A.,Åhlgren Elina Harriet,Jónsson ErlendurORCID,Yuan JunORCID,Li Ziyou Y.,Licence PeterORCID,Khlobystov Andrei N.ORCID,Alves Fernandes JesumORCID

Abstract

AbstractUsing 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.

Funder

RCUK | Engineering and Physical Sciences Research Council

RCUK | Biotechnology and Biological Sciences Research Council

Publisher

Springer Science and Business Media LLC

Subject

General Physics and Astronomy,General Biochemistry, Genetics and Molecular Biology,General Chemistry

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