Lowering the Activation Energy of Fischer Tropsch Reactions through

CoRu Core-Shell Catalysts

Mentor: Dr. Daniela Mainardi REU Student: Tosin Oyeleke

Finding the Best Catalyst for Liquid Fuel Production

Mentor: Dr. Daniela Mainardi REU Student: Tosin Oyeleke

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Methods of Producing Fuel

Fuel Production

Indirect Direct Biofuel Processes

Fischer Tropsch

Methanol Synthesis

Pyrolysis & Carbonation

Hydrogenation

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What is the Fischer Tropsch Process?

CO + H2 Catalyst Fuel + H2O

Ivo Filot et. al The Fischer Tropsch Reaction Institute of Complex Molecular Systems

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…Why Computational Modeling?

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Methodology Used

Building Catalyst Nanocluster

Nanocluster Optimization

CO docking

Energy Barrier Calculation

Molecular Dynamics

Building Catalyst Nanoclusters

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Co Core Ru Core

10% 50% 80% 10% 50% 80% 10% 50% 80% 10% 50% 80% 10% 50% 80% 10% 50% 80%

13 atoms 19 atoms 38 atoms 13 atoms 19 atoms 38 atoms

Co

Ru

-133.97eV -135.01eV -120.31eV -141.80eV -121.64eV -120.31eV

Nanocluster Optimization

Docking of CO Molecules on the Shell

Top Bridge Hollow

O   C   Co  

Daniela Mainardi Fischer-Tropsch Reactions for Fuel Production May 16,2012 8/27/13 8

Top Bridge Hollow

38 Atoms 50%

N/A

19 Atoms 50%

Docking of CO Molecules on Ru Core Nanoclusters

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13 Atoms 10%

N/A

-2.61 eV -2.98 eV -2.99 eV -1.37 eV -2.24 eV -1.96 eV -2.22 eV

-1.64 eV

38 Atoms 50% Top Bridge Hollow

19 Atoms 80%

Docking of CO Molecules on Co Core Nanoclusters

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13 Atoms 80%

N/A

-2.56 eV -3.66 eV

N/A

-1.82 eV 0.06 eV -1.24 eV -0.24 eV

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Binding Energies for Optimized CO Docked Molecules Co Core

-4

-3

-2

-1

0

1

Bin

ding

Ene

rgy

(eV

)

19atoms80% 13atoms 80% 38atoms50%

Top Bridge Hollow

LOWEST BINDING ENERGY

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Binding Energies for Optimized CO Docked Molecules Ru Core

-4

-3

-2

-1

0

Bin

ding

Ene

rgy

(eV

)

13atoms 10% 19atoms50% 38atoms50%

Top Bridge Hollow

LOWEST BINDING ENERGY

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Transition State: Energy Barriers for 13 Atoms

Reaction Pathway

Ene

rgy

(eV

)

Reactants

3.74 eV

0.17eV

Products Ea

80% Co Core Top

10% Ru Core Top

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Molecular Dynamics of 38 Atoms 50% Bridge Co Core at 25oC

FAILED

Conclusion: Favorable Adsorption Site

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-2.61 eV -2.98 eV -2.99 eV

-3.66 eV

Top Bridge Hollow

-2.56 eV

Ru Core: Co Core:

C H O Co Ru

Future Work

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• Complete transition states • Run Molecular Dynamics at 200oC • Try other CO docking positions

Ea

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My Experience so Far

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My Experience so Far

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Acknowledgement

Dr. Daniela Mainardi Fernando Soto and Suraj Gwajali Ms. Alicia Boudreaux

•  Op#ons:  solar  energy,  wind,3s  •  Introduce  the  two  core-­‐shell  structures.  •  Why  3s?  and  benefits  •  The  bo@leneck  of  using  3s  •  Our  approach  to  fix  bo@leneck  •  Our  methodology  and  results  •  Graph  of  binding  energies  (showing  the  most  pos#ve  one)  Equa#on  of  binding  energy  

•  Graph  of  transi#on  enrgies.  

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Literature Comparison of Bond Lengths

Find  •  Hydrogen  bond  length  h@p://itchem.com/calculated___and__experimental__dat  

•  CO  bond  length  •  Water  Bond  length  •  Co-­‐C  Bond  Length  h@p://sta#c.msi.umn.edu/rreports/2007/55.pdf  •  Co-­‐Co  Bond  Length  •  Co-­‐Ru  Bond  Length  

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