Understanding the reactivity of layered transition-metal sulfides: A single electronic descriptor for structure and adsorption

Charlie Tsai, Karen Chan, Jens K. Nørskov, Frank Abild-Pedersen*

*Corresponding author for this work

Research output: Contribution to journalLetterResearchpeer-review


Density functional theory is used to investigate the adsorption and structural properties of layered transition-metal sulfide (TMS) catalysts. We considered both the (1010) M-edge and (1010) 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.

Original languageEnglish
JournalJournal of Physical Chemistry Letters
Issue number21
Pages (from-to)3884-3889
Number of pages6
Publication statusPublished - 2014
Externally publishedYes

Cite this