Research Projects

Rationale of the research: The growing global energy crisis and environmental challenges have spurred intense interest in photocatalytic technologies that utilize solar energy for sustainable chemical transformations. Metal nanoclusters (MNCs), due to their tunable size, composition, and surface chemistry, offer versatile functions in photocatalysis-enhancing light harvesting, charge separation, and catalytic efficiency. Yet, issues like aggregation and low stability hinder their practical deployment. Covalent Organic Frameworks (COFs), with their high crystallinity, adjustable porosity, and strong covalent bonding, present a promising platform to anchor and stabilize MNCs. This project focuses on the rational design and synthesis of MNC@COF hybrid systems that merge the catalytic activity of nanoclusters with the structural benefits of COFs, aiming to improve performance in environmentally relevant photocatalytic processes. Scientific Objectives: • Design and synthesize atomically precise MNC-COF composites using controlled methods. • Investigate key interactions (covalent, π–π, H-bonding) between MNCs and COFs. • Enhance MNC stability within COFs and prevent aggregation during catalysis. • Evaluate and compare catalytic performance in key environmental reactions. Hypothesis/Model to be Tested: o Embedding atomically precise metal nanoclusters into functionalized COFs will create a stable and efficient hybrid system. o The COF framework offers spatial confinement to prevent cluster aggregation, while host–guest interactions (like π-π stacking and hydrogen bonding) enhance catalytic performance. o Additionally, the pore structure and linker groups are expected to fine-tune the catalytic environment, boosting activity, selectivity, and reusability. Main Experiments to be Carried Out: • COF Synthesis: Prepare known COFs using linkers rich in N, S, or O to serve as coordination sites for metal clusters. • Metal NC Preparation: Synthesize atomically precise Au, Ag, and Cu nanoclusters stabilized by thiolates, phosphines, or amino acids. These coinage metals are chosen for their accessible, size-dependent properties, chemical stability, and compatibility with COF systems. • Composite Formation: Load metal nanoclusters into COFs via post-synthetic metalation. • Characterization: o Structural: SC-XRD, PXRD, BET, FTIR o Electronic: UV-Vis, XPS, XAS o Morphological: TEM (Tomography, HAADF, EDX), ICP-MS • Photocatalytic Testing: Evaluate MNC@COF composites for pollutant degradation, CO2 reduction, and hydrogen evolution. Significance to the field of research: The proposed work aims to develop atomically precise metal nanocluster-COF composites as advanced catalysts for sustainable environmental applications. By leveraging the tunable porosity and functionality of COFs, the project enhances nanocluster stability, reactivity, and selectivity. This synergy enables efficient, reusable, and mechanistically tunable catalytic systems.