Synergistic Enhancement of Methanol Formation by Edge‐Site FeO <i> _x </i> Clusters and In‐Plane Vacancies on MoS ₂ for CO ₂ Hydrogenation

ABSTRACT MoS 2 is a promising catalyst for methanol synthesis from CO 2 hydrogenation. It is widely accepted that the in‐plane sulfur vacancies are the active sites for methanol formation, while the edge sulfur vacancies catalyze methane formation, which is typically undesirable. Rather than blocking the edge sites with heteroatom dopants, we demonstrate that decorating the edges of MoS 2 with functional FeO x clusters effectively boost methanol formation via synergy between the RWGS activity of the anchored FeO x clusters and the CO hydrogenation activity of the in‐plane sulfur vacancies. Synthetically, this was achieved by a vacuum impregnation method that chemically anchors FeO x clusters on the edges of MoS 2 , forming stable Fe‐S/Fe‐O interfaces. With these Fe‐S/Fe‐O interfaces, the Fe/MoS 2 catalyst shows markedly enhanced methanol selectivity (to 80%) and a high intrinsic space‐time‐yield (STY) of 0.6 mmol CH3OH ·m −2 ·h −1 . In situ spectroscopic and microscopic characterizations combined with theoretical calculations corroborate that the formation of amorphous FeO x clusters at edge sites of MoS 2 could effectively suppress edge S v formation, generate additional CO * , and promote the formation of methanol at the in‐plane S v sites. Broadly speaking, this work has demonstrated the modulation of MoS 2 edge sites using simple and scalable catalyst preparation methods to enhance methanol formation.