Electronic metal support interaction in electrolytes

• Applicant: Dr. Yaroslava Lykhach, Ph.D.
• Subject Area: Physical Chemistry of Solids and Surfaces, Material Characterisation ; Physical Chemistry of Molecules, Liquids and Interfaces, Biophysical Chemistry
• Term: since 2025
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 570311530

This project explores a novel strategy for modulating electrocatalytic reactions by leveraging intrinsic electric fields generated through electronic metal support interactions (EMSI) in systems comprising noble metal nanoparticles supported on reducible oxides. These EMSI-induced fields offer a stable, structurally-defined, and tunable platform for tailoring local electrochemical environments, enabling precise control over catalytic activity, selectivity, and stability in aqueous electrolytes. Unlike traditional methods that tune the electric field in the electric double layer (EDL) using solvated electrolyte species—often dynamic and hard to precisely control—EMSI offers a fundamentally different route. It provides a robust, interface-driven mechanism for engineering local electric field gradients that impact electron transfer kinetics, intermediate stabilization, and reaction pathways. By carefully designing the metal/oxide interface, we aim to establish EMSI as a predictable and controllable design parameter for electrocatalyst development. Our approach leverages model metal/oxide systems, comprising defined noble metal nanoparticles (Pt, Pd, Rh, Ru) supported on ordered Co₃O₄(111) thin films grown on Ir(100) substrates. These systems will be examined using advanced surface science techniques, including soft X-ray synchrotron radiation photoelectron spectroscopy (SRPES) and scanning probe microscopy (STM/AFM) under ultrahigh vacuum. To probe interfacial electric fields in electrochemical environments, we will use hard X-ray SRPES, electrochemical IR reflection absorption spectroscopy (EC-IRRAS), and differential electrochemical mass spectrometry (DEMS). Experimental results will be supported by density functional theory (DFT) and molecular dynamics (MD) simulations. The project is structured into three work packages (WP 1–3). In the WP 1, we will establish a comprehensive library of model metal/oxide systems with tunable EMSI through precise control over nanoparticle size, shape, and composition—as well as the oxidation state and chemical state of the oxide. In WP 2, these model systems will be used to modulate the electric field profiles within the EDL under controlled electrochemical conditions. The objective is to demonstrate that EMSI can act as a tunable lever for shaping potential landscapes at the electrode/electrolyte interface—offering nanoscale spatial resolution and unprecedented stability. In WP 3, we will explore the impact of these EMSI-induced electric field landscapes on the activity and selectivity of electrocatalytic reactions. This phase of the project will assess how local field effects—originating from carefully designed metal/oxide interfaces—can be leveraged to steer reaction pathways in a controlled and predictive manner. By connecting electric field distribution, EMSI characteristics, and catalytic performance, we aim to develop a new paradigm for the rational design of functional electrochemical interfaces.

• DFG Programme: Research Grants
• International Connection: Poland, Spain
• Co-Investigators: Professor Dr. Jörg Libuda; Dr. David Starr; Professor Dr. Dirk Zahn
• Cooperation Partners: Dr. Albert Bruix Fusté; Dr. Tomasz Sobol