Spatially Mapping Electronic Structures of Atomically Precise Copper Nanoclusters Using Advanced Crystallography

University Of Illinois At Chicago, Chicago IL

Investigators

Abstract

With support from the Chemical Mechanism, Function, and Properties Program of the Division of Chemistry, Professor Neal Mankad at the University of Illinois Chicago is investigating small, well-defined clusters of copper atoms. These clusters can help scientists better understand nano-catalysts — materials that play vital roles in speeding up chemical reactions in both industry and research but are often difficult to study because their structures are not well understood. This project uses advanced X-ray techniques to map where electrons are located within these copper clusters, revealing how the arrangement of atoms affects their chemical behavior. By learning how electrons are distributed, scientists gain valuable insights that can help design better catalysts. This work sits at the intersection of physical, inorganic, and materials chemistry and offers top-tier training opportunities for students and researchers at all stages. Copper (Cu) catalysts are widely used to promote reactions including, but not limited to, hydrogenation and electroreduction of carbon dioxide. However, the active sites in these heterogeneous systems are often structurally ill-defined and difficult to probe with atomic-level precision. This project is guided by the central hypothesis that resolving the electronic structures of individual Cu atoms within atomically precise nanoclusters (APNCs) will enhance understanding by enabling correlations between molecular electronic structure and the local environments present in bulk materials. The objective is to apply advanced crystallographic methods spatially to map the electronic structures of Cu-rich APNCs, providing an atom-level understanding of chemical bonding as a function of molecular structure. This research is designed to address three key questions: 1) How do the atom-specific electronic structures of Cu sites vary across a series of APNCs, as revealed by resonant X-ray diffraction anomalous fine structure (DAFS)? 2) What are the quantitative bonding characteristics of “cuprophilic” Cu···Cu interactions, based on high-resolution charge density (HRCD) analyses and atoms-in-molecules (AIM) theory? 3) How do heterometal dopants influence the electronic structures of Cu nanoclusters, as assessed through Cu K-edge DAFS? This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.