Engineering Active Sites for Sustainable Catalysis

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Engineering Active Sites for Sustainable
Catalysis

• Robert Raja

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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
  (CH activation)
• High thermal stability/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, 517519
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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

1. Photocatalytic-splitting of water for the
   generation of H2 and O2
2. Harvesting marine-energy for potential impact on
   H2 economy

Engineering Perspective

1. Developing marine exhaust-gas cleaning
   technologies
2. 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

• Role in Future Challenges
• Sustainable energy
• Atom-efficient Catalysis
• Benign Reagents
• Eliminate Waste
• Renewable Fuels

• Renewable Transport Fuels
• Bio-Ethanol Biomass Conversions
• Hybrid Biofuels (1st and 2nd generation)
• Bio-diesel

Dalton Trans., 2012, 41, 982-989
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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

• 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