Engineering Active Sites for Sustainable Catalysis

1. Engineering Active Sites for Sustainable Catalysis Robert Raja

2. Engineering Active Sites for Enhancing Catalytic Synergy Porous Molecular Frameworks • 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 • 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 Industrial Research Projects Bulk Chemicals & Energy • Properties: • Hybrid/hierarchical architectures. • 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 thermalstability/recyclability • Structure-property relationships • Greener Nylon • Terephthalate-based fibres • Liquid-phase Beckmann reactions • -Caprolactam synthesis • Bio-Ethanol dehydration Fine-Chemicals & Pharmaceuticals • Cascade Reactions & Flow Chemistry • Vitamins • Agrochemicals • Fragrances and flavours • Food-additives Chem. Commun., 2011, 47, 517–519

3. Clean drinking water Catalysis Renewable energy CO2 capture Sustainable Catalysis For Renewable Energy Applications: • 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 Photocatalytic-splitting of water for the generation of H2 and O2 Harvesting marine-energy for potential impact on H2 economy Role in Future Challenges • Sustainable energy • Atom-efficient Catalysis • Benign Reagents • Eliminate Waste • Renewable Fuels Engineering Perspective Developing marine exhaust-gas cleaning technologies Selective catalytic reduction for removal on NOx, SOx, VOCs, particulates from diesel engines Research Areas • Hydrogen Economy • Industrial Hydrogenations • Low-temperature acid catalysis • Alternatives to PGM Catalysts • Renewable Transport Fuels • Bio-Ethanol & Biomass Conversions • Hybrid Biofuels (1st and 2nd generation) • Bio-diesel Dalton Trans., 2012, 41, 982-989

4. Hybrid Catalysts for Biomass Conversions and Multifunctional Hierarchical Architectures for Biodiesel Production Single-Step Cascade Reactions for the Conversion of Vegetable Oils to FAMES & Direct Glycerol conversion to 1,3-propanediol Synergy Bio-Ethanol/ Propanol Ethylene/Propylene • Academic & Industrial Partnership Programs • Renewable Transport Fuels • Bio-Ethanol and Biomass Conversions • Hybrid Biofuels (1st and 2nd Generation) • Biodiesel & Bioenergy • Hydrogen Economy • Alternatives to PGM Catalysts • Industrial Hydrogenations • Low-Temperature Acid-Catalysis • Renewable Polymers