Computational catalysis for sustainability Evgeny Pidko

Transcription

1 SURFsara Data & Computing Infrastructure Event Amsterdam March 13, 2014 Computational catalysis for sustainability Evgeny Pidko

2 Inorganic Materials TU/e IMC Chair: prof. dr. ir. E.J.M. Hensen Topics Molecular Heterogeneous Catalysis Predictive Catalyst Design Expertise Catalysis Synthesis Reaction mechanism In situ spectroscopy Renewable resources Sustainable Energy Sustainable Energy Technologies Asst. Prof.: Dr. E.A. Pidko Approach From molecular understanding to rational catalyst design

3 Catalysis for sustainability Options: biomass, carbon dioxide, water, etc to replace oil ~100 years of HC refinery Infancy of biorefinery From oil to renewables: - different chemistry - new catalysts needed - transition on a short term Understanding guides catalyst design

4 Towards rational catalyst design Asst. Prof.: Dr. Evgeny A. Pidko I: Making fossil-based chemistry greener II: CO 2 valorization III: Catalytic chemistry of biomass Theory - Reaction mechanism - Multiscale modeling - Design rules State-of-the art spectroscopy - In situ characterization - Catalyst at work Synthesis - Inorganic chemistry - Molecular heterogeneous catalysis - (Micro-) porous materials

5 Theory of catalysis Heterogeneous catalysis Definition: the phase of catalyst differs from that of reactants More to that: heterogeneity of the catalyst itself reactants catalyst products What exactly catalyzes the reaction? What is the reaction mechanism? What can we do to improve the properties? Without molecular understand we can just try and fail/succeed

6 Complexity in catalysis Heterogeneous catalysis Catalyst support HetCat Introduction of the active phase Homogeneous catalysis Structural & mechanistic ambiguity

7 HetCat: Chemistry of Fe in zeolites Fe/ZSM-5 Green process for phenol production Efficient denox for clean air Heterogeneous catalysis Quantum chemistry: DFT: PBE functional+vdw Model: periodic boundary conditions MFI unit cell (>300 atoms) different Fe different positions electronic configuration Panov et al. J. Mol. Catal. 61 (1990) 85 Panov et al. Cattech 4 (2000) 18; Arends, Sheldon et al. J.Catal. 195 (2000) 287; Zhu, Hensen et al., Chem. Comm. (2002); Hensen et al. J. Catal. 233 (2005) 123 & 136; Li, Hensen et al., Chem. Comm. (2008); Xin, Hensen et al., Chem. Commun. (2009)

8 Unraveling structural complexity Zeol + Fe sourc e DFT calculations Ab initio thermodynamics Dominant species identified State of Fe in FeZSM-5 is determined during preactivation J. Phys. Chem. C 2013, 117, 413

9 Reaction order Rate of formation Fraction of intrazeolite complexes Macroscopic description DFT calculations How does catalyst work? Which step controls the rate? Link to experiment Process design rules J. Catal. 2013, 308, n(n 2 O) Microkinetic modeling Temperature / K Temperature / K 0 N N 2 O@[Fe(O) 2 FeO] [Fe( O) 2 FeO] 2+ [Fe( O) 2 Fe] 2+ [Fe( O)Fe] 2+ all other species Temperature / K

10 HomCat: CO 2 as C1 building block CO 2 capture & conversion +C 2 H 4 CH 2 =CHCOOH acrylic acid CO 2 can be coupled with C 2 H 4 Cannot be performed in a catalytic manner Nickelalactone 4 is the end product DFT calculations to determine the key parameters of the successful catalytic system 10 Ministry for innovation, science and research of the german State of North Rhine-Westfalia

11 Can classical HomCat help? Ligand scope Nickelalactone 4 is the end product Ligand effect only minor Alternative path is needed ChemCatChem 2014, 6, 800

12 Bifunctional catalysis for CO 2 conversion Reaction path engineering DFT predict high potential of a bifunctional catalysis A new technology has been developed D. Vogt, C. Hendriksen, E. Pidko, B. Schäffner, M. Blug EU Patent Appl , 2013 Yang, Pidko et al, ChemCatChem 2014, 6, 800

13 Future: dynamics in chemocatalysis isomerization dehydration glucose fructose - Polymers - Solvents - Fuel components - etc Enzymatic catalysis: Tailor-made reaction environment Multifunctional catalyst Homogeneous catalysis: Transient self-organization of active complexes Solvent-assisted conversion Heterogeneous catalysis: Cooperative catalysis Confinement effect Dynamics in confinement space Angew. Chem. In. Ed. 2010, 49, 2530 ChemCatChem 2012, 4, 1263 ChemSusChem 2013, 9, 1688

14 Summary Key role of HPC in modern catalysis Predictive power of state-of-the-art chemical theory Synergy between theory and experiment Computations to engineer new processes Complexity and dynamics in chemocatalysis Molecular insight to control catalytic reactivity