Sulfur Moiety as a Double-Edged Sword for Realizing Ultrafine Supported Metal Nanoclusters with a Cationic Nature

Heterogeneously and uniformly dispersed metal nanoclusters with high thermal stability and stable nonmetallic nature show outstanding catalytic performance. In this work, we report on the role of sulfur moieties in hydrochlorination catalysis over carbon-supported gold (Au/C). A combination of experimental and theoretical analyses shows that the -SO₃H and derived -SO₂H sulfur species in high oxidation states at the interface between Au and -SO₃H at ≥180 °C give rise to high thermal stability and catalytic activity. By contrast, the grafted thiol group (-SH) and the derived low-valence sulfur species on carbon markedly destabilize the Au nanoclusters, promoting their rapid sintering into large Au nanoparticles and leading to the loss of their cationic nature. Theoretical calculations suggest that -SO₃H favorably adsorbs and stabilizes cationic Au species. Compared to Au/C and Au-SH/C with the Au^α+/Au⁰ atomic ratios of 1.02 and 0.24, respectively (α = 1 or 3), the activity and durability of acetylene hydrochlorination are remarkably enhanced by the interaction between the -SO₃H moieties and cationic Au species that enables the high oxidation state of Au to be effectively retained (Au^α+/Au⁰ = 3.82). These results clearly demonstrate the double-edged sword effect of sulfur moieties on the catalytic Au component in acetylene hydrochlorination. The double-edged sword effect of sulfur species in the stabilization/destabilization of metal nanoclusters is also applicable to other metals such as Ru, Pd, Pt, and Cu. Overall, this study enriches the general understanding of the stabilization of metal clusters and provides insight into a wet chemistry strategy for stabilizing supported ligand-free nanoclusters.