Robert Raja: Research Themes 2011/2  Cascade Reactions & Flow Chemistry  Vitamins  Agrochemicals  Fragrances and flavours  Food-additives Porous Molecular Frameworks The Strategy:  Designing novel framework structures (zeolites, AlPOs, MOFs, ZIFS).  Isomorphous substitution of framework anions and cations with catalytically active transition-metal entities.  Take advantage of pore aperture for shape-, regio- and enantio-selectivity Properties:  Wide-ranging chemical properties  Redox catalysis (selective oxidations, epoxidation).  Acid catalysis (alkylations, isomerisations, dehydration).  Bifunctional and cascade reactions  Oxyfunctionalization of alkanes and aromatics (C–H activation)  High thermal stability/recyclability  Active sites readily characterized.  Structure-property relationships  Greener Nylon  Terephthalate-based fibres  Polyamides   -Caprolactam  Bio-Ethanol dehydration Fine-Chemicals & Pharmaceuticals Applications Bulk Chemicals & Energy Key Benefits:  Replace highly corrosive and more expensive oxidants with benign ones (molecular oxygen)  Access mechanistic pathways that were hitherto difficult  Synergy in catalytic transformations  Catalyst and process conditions amenable for industrial exploitation Chem. Commun., 2011, 47, 517–519 Engineering Active Sites for Enhancing Catalytic Synergy

Role in the Grand Challenges Sustainable energy Atom-efficient Catalysis Benign Reagents Eliminate Waste Renewable Fuels Renewable energy Clean drinking water CO 2 capture Sustainable Catalysis For Renewable Energy Applications: Research Areas  Renewable Transport Fuels  Bio-Ethanol & Biomass Conversions  Hybrid Biofuels (2 nd and 3 rd generation)  Bio-diesel  Hydrogen Economy  Industrial Hydrogenations  Low-temperature acid catalysis  Alternatives to PGM Catalysts Hybrid/Hierarchical Porous Architectures Key Benefits:  Better compositional control compared to traditional methods such as incipient wetness and deposition/precipitation  Improved site-isolation aids catalytic turnover  Use of oxophile reduces amount of noble metals and aids anchoring  Exceptional synergy in catalytic reactions (akin to enzymes)  Access mechanistic pathways that were hitherto difficult  Process conditions amenable for industrial exploitation Collaborative Projects 1.Photocatalytic-splitting of water for the generation of H 2 and O 2 2.Harvesting marine-energy for potential impact on H 2 economy Engineering Perspective 1.Developing marine exhaust- gas cleaning technologies 2.Selective catalytic reduction for removal on NOx, SOx, VOCs, particulates from diesel engines Dalton Trans., 2012, 41, Robert Raja: Research Themes 2011/2

Functionalised OrganoCatalysis Catal. Sci. Technol., 2011, 1, Engineering Active Sites for Enhancing Catalytic Synergy L-lysine Must have these functionalities accessible for catalysis to occur. Substrate binding Support binding The Strategy:  Innovative “click- chemistry” and solid- phase peptide synthesis for creating unique, isolated single-sites  Unique functionalities for substrate and support binding  Bifunctional and multifunctional sites for synergy Features:  Mechanistic pathway can be understood at a molecular level  Catalysts designed for specific target reactions – potential to optimise and modify support characteristics  High stereo/enantio control Key Benefits:  Specific binding of organocatalyst to support ensures optimal orientation  Lower mol % used  Recovery and recyclability  Atom efficiency  No loss of expensive catalyst  Stability and versatility Perceived Impact:  Structure-property relationships  Utilised in a range of organic transformations involving enamine intermediates  Industrially significant C=C and C=O hydrogenation reactions  Relatively higher enantioselectivities compared to homogeneous analogues

Robert Raja: Research Themes 2011/2 Bioinspired Catalysts The Strategy:  Molecular fragments circumscribing the active site anchored or encapsulated within a porous host.  Attachment through side-chain – hence functional groups are accessible for catalysis  Active sites can be covalently attached through solid-phase peptide synthesis Properties:  Environment of active site can influence stereo-selectivity of final product  Functional mimics of enzymes  Isolated single-sites for efficient catalytic turnover  Increased solvent and pH versatility  Facile recovery and recyclability Key Benefits:  The hydrophilicity/hydrophobicity of the catalyst can be suitably tailored to enhance activity and selectivity  Structural and conformational flexibility of ligands  Take advantage of concavity of pore – induce chiral catalysis  Lower mol % of catalyst required Applications:  Generalised strategy for anchoring highly active and selective bioinspired complexes  Catalyze a range of oxidations that are of industrial significance: benzylic alcohols, hydrocarbons, aromatics, sulfides  Selective oxidations and epoxidations using molecular oxygen Chem. Commun., 2010, 46, Engineering Active Sites for Enhancing Catalytic Synergy