Fundamental Properties of Surface Sys Tailoring surface chemical properties using electronic structure theory Frank Abild-Pedersen

Energy efficient fuel synthesis Sustainable energy through catalysis Energy efficient fuel synthesis Better catalysts required Efficient Stable Made from Earth-abundant elements

SUNCAT mission To develop understanding of interface phenomena To develop science-based design of catalysts To apply methods to interfaces of interest in energy transformations To close the theory-synthesis - characterization-test loop

Top-down approach Nørskov, Bligaard, Rossmeisl, Christensen Nature Chem. 1, 37 (2009)

Syngas to fuels Less sensitivity to feed stock compared to other bio-routes. Anything can be gasified. Syn CO + H2 National Energy Technology Laboratory: www.netl.doe.gov Williams, R. H. et. al.; Energy Sust. Dev.; 1; 18-34; 1995 Methane (CH4) Methanol (CH3OH), Dimethyl ether Syngas CO+H2 Higher alcohols C2H5OH, etc. Fischer Tropsch (CxHy)

Cu(211) Methanol pathway CO + 2H2 = CH3OH ΔE (eV) COH* COH*+H*

Abild-Pedersen et al. Phys. Rev. Lett. 2007, 99, 016105. Tools – reducing the parameter space BEP Relations Scaling Relations Abild-Pedersen et al. Phys. Rev. Lett. 2007, 99, 016105. Bligaard et al. J. Catal 2004, 224, 206.

CO + 2 H2 -> CH3OH Methanol microkinetics (1) CO(g) + * -> CO* (2) H2(g) + 2* -> 2 H* (3) CO* + H* -> HCO* + * (4) HCO* + H* -> H2CO* + * (5) H2CO* + H* -> H3CO* + * (6) H3CO* + H* -> CH3OH(g) + 2* All reaction energies --> described in terms of the carbon and oxygen binding energies All activation barriers --> described in terms of the carbon and oxygen binding energies --> two parameters describe everything ! --> construction of activity volcano

Methanol activity volcano Rate 513 K 40 bar CO 40 bar H2 log (TOF) s-1

Screening

Connecting dft with industrial catalyst design Screening Rate 573 K 313 K Connecting dft with industrial catalyst design Jacobsen et al. J. Catal. 2002, 205, 382.

New catalyst leads

Higher/lower gallium content results in decreased activity Preliminary experimental tests Activity of Ni5Ga3/SiO2 comparable with Cu/ZnO/Al2O3 at 1 bar Higher/lower gallium content results in decreased activity Cu/ZnO/Al2O3 catalyst has 100% selectivity NinGam/SiO2 catalysts exhibit decreased selectivity at higher temperatres