Comparative atomic-scale analysis of promotional effects by late 3d-transition metals in MoS 2 hydrotreating catalysts

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The promotion of the activity of MoS 2-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 MoS 2, 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 MoS 2 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 MoS 2-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 MoS 2. 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.