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

DOI: 10.1038/s41467-021-25263-6 DOI Help

Authors: 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 Jónsson (University of Cambridge; Chalmers University of Technology) , Jun Yuan (University of York) , Ziyou Y. Li (University of Birmingham) , Peter Licence (University of Nottingham) , Andrei N. Khlobystov (University of Nottingham) , Jesum Alves Fernandes (University of Nottingham)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Nature Communications , VOL 12

State: Published (Approved)
Published: August 2021
Diamond Proposal Number(s): 19850 , 17198

Open Access Open Access

Abstract: 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.

Journal Keywords: Catalyst synthesis; Catalytic mechanisms; Heterogeneous catalysis

Subject Areas: Chemistry


Instruments: B18-Core EXAFS

Added On: 23/08/2021 08:31

Documents:
s41467-021-25263-6.pdf

Discipline Tags:

Physical Chemistry Catalysis Chemistry Chemical Engineering Engineering & Technology Nanoscience/Nanotechnology

Technical Tags:

Spectroscopy X-ray Absorption Spectroscopy (XAS) Extended X-ray Absorption Fine Structure (EXAFS) X-ray Absorption Near Edge Structure (XANES)