Project Description

The Ph.D. project aims to develop transition-metal sulfide and oxide clusters encapsulated in microporous supports as efficient hydrogenation catalysts. H2 activation is a critical step in numerous (industrial) processes, including hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrodeoxygenation (HDO), CO2 hydrogenation, and biomass upgrading. Conventional catalysts often suffer from low selectivity, deactivation, and poor atomic efficiency. Encapsulating atomically precise metal sulfide/oxide clusters within microporous frameworks offers a powerful strategy to stabilize active phases, improve atomic efficiency, tune electronic properties, and achieve precise control over catalytic behavior.

This project will focus on the synthesis of well-defined transition-metal sulfide and oxide clusters encapsulated within microporous materials such as zeolites and metal-organic frameworks (MOFs). The influence of framework topology, acidity, and composition on cluster formation, dispersion, and confinement effects will be systematically investigated. Particular emphasis will be placed on understanding how cluster size, spatial confinement, and metal-support interactions govern H2 adsorption, dissociation pathways (homolytic vs heterolytic), and hydrogen spillover.

Advanced synthesis strategies, such as chemical vapor deposition and in situ sulfidation/reduction/oxidation, will be employed to achieve controlled encapsulation and homogeneous dispersion. Catalytic performance will be evaluated in reactions including HDS, HDN, hydrodeoxygenation (HDO), and CO2 hydrogenation. State-of-the-art characterization techniques, including operando spectroscopy (IR, Raman, XAS) and high-resolution electron microscopy, will be used to identify active sites and track structural evolution under reaction conditions. The project will involve periodic visits to synchrotron facilities for advanced operando measurements (XAS/XES) to obtain molecular-level insights into catalyst structure and dynamics.