Catalytic Transformations of 1-Butene over Palladium. A Combined Experimental and Theoretical Study

Applying a density functional approach to slab models of planar, (111), and rough, (110), Pd surfaces, we determined the isomerization free energy barriers of 1-butene to be significantly lower than the hydrogenation barriers. Microkinetic modeling allows one to mirror the kinetic experiments on conversions of 1-butene at the corresponding single-crystal surfaces in a qualitative fashion. Despite the inherent limitations of such kinetic modeling, theoretical predictions are fully supported by experimental data using Pd model catalysts: i.e., Pd(111) and Pd(110) surfaces. The isomerization mechanism was calculated to proceed via an initial dehydrogenation of 1-butene to 1-buten-3-yl as an intermediate—in contrast to the commonly proposed 2-butyl intermediate, associated with the Horiuti–Polanyi mechanism. Our modeling results rule out the original assumption that isomerization has to start with a hydrogenation step to rationalize the dependence of isomerization on hydrogen. However, this hydrogen dependence may arise in the second step, after an initial dehydrogenation, as suggested by the experimental data under hydrogen-deficient conditions.J.S.-A. acknowledges financial support by Generalitat Valenciana (BEST/2007/045) and MEC/OEAD (Acciones Integradas HU2006-002) supporting a research stay in Vienna. This work was supported by grant no. 1527700033 of the A*STAR Science and Engineering Research Council as well as generous allotments of computational resources at the National Supercomputing Center Singapore and the A*STAR Computational Resource Center