Understanding the Reactivity of Layered Transition-Metal Sulfides: A Single Electronic Descriptor for Structure and Adsorption.
Density functional theory is used to investigate the adsorption and structural properties of layered transition-metal sulfide (TMS) catalysts. We considered both the (101̅0) M-edge and (1̅010) S-edge terminations for a wide range of pure and doped TMSs, determined their sulfur coverage under realistic operating conditions (i.e, steady-state structures), and calculated an extensive set of chemisorption energies for several important reactions. On the basis of these results, we show that the d-band center, εd, of the edge-most metal site at 0 ML sulfur coverage is a general electronic descriptor for both structure and adsorption energies, which are known to describe catalytic activity. A negative linear correlation between adsorbate-S binding and S-metal binding allows εd to describe the adsorption of species on both metal and sulfur sites. Our results provide a significant simplification in the understanding of structure-activity relationships in TMSs and provides guidelines for the rational design and large-scale screening of these catalysts for various processes.
†Department of Chemical Engineering, Stanford University, Stanford, California 94305, United States.|‡SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States.
Charlie
C
Tsai
†Department of Chemical Engineering, Stanford University, Stanford, California 94305, United States.|‡SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States.
Karen
K
Chan
†Department of Chemical Engineering, Stanford University, Stanford, California 94305, United States.|‡SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States.
Jens K
JK
Nørskov
‡SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States.
Frank
F
Abild-Pedersen
adsorption; catalysis; density functional theory; edge structure; transition-metal sulfide