Comparative atomic-scale analysis of promotional effects by late 3d-transition metals in MoS2 hydrotreating catalysts

The promotion of the activity of MoS2-based hydrotreating catalysts by various first-row transition metals exhibits a typical variation referred to as a volcano plot. Co and Ni are seen to substantially promote the catalytic activity of MoS2, whereas the neighboring first-row metals promote reactivity to a much lesser extent, or not at all. In order to provide a better atomistic understanding of the catalytic synergies, we perform here a comparative scanning tunneling microscopy (STM) analysis of the atomic-scale structure and morphology of MoS2 nanoclusters doped with the first-row transition metals: Fe, Co, Ni, and Cu. We reveal that addition of all four dopant metals results in the formation of mixed-metal Co-Mo-S-type structures shaped as single-layer hexagonally truncated triangular MoS2-like nanoclusters. The modification of the preferred nanocluster equilibrium morphology is explained as a direct consequence of a favored substitution of dopant metal atoms into the S-edges of MoS2. The degree of truncation and the edge dispersion are, however, found to depend greatly on the type of dopant atom since the relative length of the dopant-stabilized edges decreases with the number of valence shell electrons of the dopant transition metal. A comparison of the observed atomic structure and morphology with the hydrotreating activity measured for industrial-style prepared Me-Mo-S catalysts (Me = Fe, Co, Ni, and Cu) supported on carbon reveals that two parameters are relevant to describe the promotional behavior: (i) a geometric parameter, which relates to the relative number of promoted and unpromoted sites in the Me-Mo-S nanoclusters, and (ii) a more conventional parameter relating to bonding and adsorption strength, i.e., describing the intrinsic activity of the particular Me-doped S-edge. (C) 2010 Elsevier Inc. All rights reserved.