Computational catalysts design for non- transitional...
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Poul Georg Moses
Computational catalysts design for non-transitional metal catalysts
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Research and development at HTAS GIER 1 at HTAS ca. 1960 Basic Research
Fundamental Studies Catalyst Characterisation
Industry
Scale-up Pilot Operation
Computer Modelling
Catalyst Formulation
Process Development
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Standard tools in design of metal based catalysts Thermodynamics
(Micro)kinetic modeling
Data bases of DFT values
(Linear) correlations to fill the gaps
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Standard tools applied to non-metal systems ZnO as a methanol catalysts
Trends in HDS catalysis
S Mo Co
Co9S8
MoS2-like nanoparticles ”Co-Mo-S”
Co:Al2O3
Al2O3 (alumina) support
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Methanol synthesis Cu/ZnO/Al2O3
T= 220 – 300 °C ,
P=50 – 100 Bar
CO(g) + 2H2(g) ->CH3OH(g)
CO2(g) + 3H2(g) ->CH3OH(g) +H2O(g)
H2O(g) + CO(g) -> CO2(g) + H2(g) (Water gas shift)
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Cu/ZnO/Al2O3 Energy filtered TEM imaging
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Three important questions in MeOH catalysis 1. What affects the stability of MeOH Cat.?
2. Is MeOH formed from CO, CO2 or both?
3. What is the role of ZnO in MeOH catalysis?
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ZnO as a methanol catalysts
ZnO original Methanol catalysts
T= 600 – 700 °C , P=200 – 300 Bar
CO(g) + 2H2(g) ->CH3OH(g) Dominating pathway
CO2(g) + 3H2(g) ->CH3OH(g) +H2O(g)
H2O(g) + CO(g) -> CO2(g) + H2(g) (Water gas shift)
M. Kurtz, J. Strunk, O. Hinrichsen, M. Muhler, K. Fink, B. Meyer, and C. Wöll. Angew. Chem. Int. Ed. 2005, 44, 2790
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Methods RPBE vs. BEEF
a) F. Studt, F. Abild-Pedersen, J.B. Varley, J.K. Nørskov Catal. Lett 143, 2012, 71
Approach – Determine model surface
– Calculate reaction thermodynamics
– Estimate reaction barriers
– Analyze with kinetic model
Details – Use GPAW+BEEF-vdW
– Use Shomate equation (harmonic approx.) for gas (adsorbate) thermal contribution.
– Apply O=C=O correction for gas phase HCOOH,CO2,H2
a)
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Model Surface ZnO(100) ~1.8 J/m2
ZnO(110) ~1.9 J/m2
ZnO(001) ~3.5 J/m2
ZnO(00-1) ~4.3 J/m2
Diebold, App. Surf. Sci. 237 (2004)
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Model Surface ZnO(100) ~1.8 J/m2
ZnO(110) ~1.9 J/m2
ZnO(001) ~3.5 J/m2
ZnO(00-1) ~4.3 J/m2
Not stable! Reconstruction is controversial…
Diebold, App. Surf. Sci. 237 (2004)
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Model Surface
Assume scaling relations are similar to metals
Use O and CO binding as probes for reactivity of surfaces
Nothing
MeOH Methane
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Model Surface Non-polar surfaces are
more noble than gold!
Zn-terminated 001 surface looks interesting
Defects on (001) are likely too reactive
Defects on non-polar surfaces could be interesting, but complex to model.
Nothing
MeOH Methane
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Barrier Estimation
Take available barriers from literature – Calculated with PBE/LCAO
Use transition-state scaling to estimate few remaining barriers
Very crude and very fast
Trends hold as long as barriers don’t change RDS
Y. Zhao, R. Rousseau, J. Li, D. Mei J. Phys Chem C 116, (2012) 15952 G. K. Smith, S. Lin, W. Lai, A. Datye, D. Xie, H. Guo, Surface Science 605 (2011) 750
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CO Hydrogenation: CO + H2 → CH3OH
RDS appears to be methoxy removal
CO hydrogenation appears very facile… why are high temperatures needed?
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CO2 Hydrogenation:
Formic acid route is high in energy
Formate species are very stable
Mechanism is not clear
CO2 + 3H2 → CH3OH + H2O
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Water Gas Shift CO+ H2O ->CO2 + H2
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Free energy diagram algebra
+ + =
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Free Energy Spaghetti Diagram
Need a method for gaining intuition from complex reaction network!
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Micro-kinetic model CO2 hydrogenation CO hydrogenation
CO:H2 = 7:1, PCO2 = 0.001 %, 1% of equilibrium conversion to MeOH and H2O
CO hydrogenation is dominant for ZnO
High temperatures and pressures are needed for significant rates
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Rate-limiting Steps
Rate-limiting step changes between formaldehyde and methoxy hydrogenation for CO hydrogenation
Formate or OCH2OH decomposition is rate-limiting for CO2 hydrogenation
CO hydrogenation CO2 hydrogenation
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CO2 poisoning is due to strong formate binding
Rate is not just CO + CO2 hydrogenation!
Site competition is important
CO2 Poisoning
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Conclusions on methanol synthesis over ZnO
Polar surfaces of ZnO are likely the most important for catalysis
Kinetic models provide an intuitive way of analyzing complex reaction networks
MeOH synthesis is limited by removal of formate from the surface, leading to high temperature/pressure requirements and low CO2 concentrations
Andrew Medford; Jens Sehested, Jan Rossmeisl, Ib Chorkendorff, Felix Studt, Jens K Nørskov, Poul G Moses, Journal of catalysis, accepted
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Trends in HDS catalysis over sulfides
Provide guidelines
Identify key descriptors
Ultimately predict
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Green is very dirty Pyrolysis oil contain 0-0.05wt % S
EU and US regulations are 0.0010-0.0015 wt % S in diesel
Hydrotreating is needed
A. Oasmaa, E. Kuoppala, D.C. Elliott Energy and Fuels, 2012,26,2454
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Hydrodesulfurization (HDS)
(Sulfur-containing organic compound) + H2 → (Desulfurized organic
compound) + H2S
thiophene
dibenzothiophene
4,6-dimethyl dibenzothiophene
Naphta: 1.4-5.2 MPa, 290-370 °C
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Catalysts structure
Co, Ni Promoters is located at the S edge
S Mo Co
Co9S8
MoS2-like nanoparticles ”Co-Mo-S”
Co:Al2O3
Al2O3 (alumina) support
H. Topsøe, B.S. Clausen, R. Candia, C. Wivel, S. Mørup, J. Catal. 68 (1981) 433
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Atomic scale structural insight : STM confirms DFT prediction
J.V. Lauritsen, M.V. Bollinger, E. Lægsgaard, K.W. Jacobsen, J.K. Nørskov, B.S. Clausen, H. Topsøe, F. Besenbacher J. Catal 221 (2004) 510
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Atomic scale structural insight Transmission electron microscopy
L.P. Hansen, Q.M. Ramasse, C. Kisielowski, M. Brorson, E. Johnson, H. Topsøe, and S. Helveg. Angew. Chem. Int. Ed. 2011, 50 10153
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STEM confirms DFT prediction
Edge structure depends on (T,p) of the H2,H2S atmosphere Synthesis: PH2 = 0.9bar, PH2S = 0.1bar at 1073K. Storage: N2 at 300K
Mo edge S edge
Bollinger, Jacobsen, Nørskov, Phys. Rev. B 67, 085410 (2003).
Synthesis (1073K)
Quenched state(300K)
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Trends in HDS activity Several models based on bulk properties.
H. Topsøe, K. G. Knudsen, L.S. Byskov, J. K. Nørskov, B. S. Clausen Sci. Tech. Cat. 1998 p13
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Schematic potential energy diagram
P.G. Moses, B. Hinnemann, H. Topsøe, J.K. Nørskov, J. Catal 248 (2007) 188, 260 (2008) 202 P.G. Moses, B. Hinnemann, H. Topsøe, J.K. Nørskov, J. Catal 268 (2009) 201
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HDS kinetics: Hydrogenation path
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HDS kinetics: Direct desulfurization path
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Linear Correlations
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Sabatier analysis Assume
– Optimal coverage
))/exp(),/min(exp())max(),min(max(22
TkETkErateraterate BSHBSCSHSC −−=∝
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Compounds
)(22
1 eVEHH −µ
µ H-1
/2E
H2(e
V)
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Activity Volcano
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Predict known excelent catalysts
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Conclusion on trends in HDS catalysis Effect of Co Promotion
Towards a predictor of HDS activity
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Summary Thermodynamics
(Micro)kinetic modeling
Data bases of DFT values
(Linear) correlations to fill the gaps
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Acknowledgements
DTU – Ib Chorkendorff
– Jan Rossmeisl
Stanford – Jens Nørskov
– A. J. Medford
– L. Grabow
Aarhus
– J.V. Lauritsen, F. Besenbacher
Governments – Danish National Research
Foundation
– National Science Foundation