Pritzi Marco, Pascher Tobias F, Grutza Marie-Luise, Kurz Philipp, Ončák Milan, Beyer Martin K
Institut für Ionenphysik und Angewandte Physik, Universität Innsbruck, Technikerstrasse 25, 6020 Innsbruck, Austria.
Institut für Anorganische und Analytische Chemie, Albert-Ludwigs-Universität Freiburg, Albertstrasse 21, 79104 Freiburg, Germany.
J Am Soc Mass Spectrom. 2022 Sep 7;33(9):1753-1760. doi: 10.1021/jasms.2c00162. Epub 2022 Jul 29.
Molybdenum sulfides are considered a promising and inexpensive alternative to platinum as a catalyst for the hydrogen evolution reaction. In this study, we perform collision-induced dissociation experiments in the gas phase with the halogenated molybdenum sulfides [MoSCl], [MoSBr], and [MoSI]. We show that the first fragmentation step for all three dianions is charge separation via loss of a halide ion. As a second step, further halogen loss competes with the dissociation of a disulfur molecule, whereas the former becomes energetically more favorable and the latter becomes less favorable from chlorine via bromine to iodine. We show that the leaving S group is composed of sulfur atoms from two bridging groups. These decomposition pathways differ drastically from the pure [MoS] clusters. The obtained insight into preferred dissociation pathways of molybdenum sulfides illustrate possible reaction pathways during the activation of these substances in a catalytic environment.
硫化钼被认为是一种有前景且廉价的替代铂的析氢反应催化剂。在本研究中，我们对卤化硫化钼[MoSCl]、[MoSBr]和[MoSI]进行了气相碰撞诱导解离实验。我们表明，所有三种二价阴离子的第一步碎片化是通过卤离子的损失进行电荷分离。第二步，进一步的卤素损失与二硫分子的解离相互竞争，而从氯到溴再到碘，前者在能量上变得更有利，后者则变得不太有利。我们表明，离去的S基团由来自两个桥连基团的硫原子组成。这些分解途径与纯[MoS]簇有很大不同。对硫化钼优选解离途径的深入了解揭示了这些物质在催化环境中活化过程中可能的反应途径。
