Sulfur doped in carbon matrix can tether metal atoms to form high-loading atomically dispersed supported metal catalysts.

Intermetallic catalysts are of immense interest, but how heterometals diffuse and related interface structure remain unclear when there exists a strong metal-support interaction. Here, we developed a kinetic diffusion–controlled method and synthesized intermetallic Pt 2 Mo nanocrystals with twin boundaries on mesoporous carbon (Pt 2 Mo/C). The formation of small-sized twinned intermetallic nanocrystals is associated with the strong Mo-C interaction–induced slow Mo diffusion and the heterogeneity of alloying, which is revealed by an in situ aberration-corrected transmission electron microscope (TEM) at high temperature. The twinned Pt 2 Mo/C constitutes a promising CO-resistant catalyst for highly selective hydrogenation of nitroarenes. Theoretical calculations and environmental TEM suggest that the weakened CO adsorption over Pt sites of Pt 2 Mo twin boundaries and their local region endows them with high CO resistance, selectivity, and reusability. The present strategy paves the way for tailoring the interface structure of high–melting point Mo/W-based intermetallic nanocrystals that proved to be important for the industrially viable reactions.

Supported bimetallic nanocluster catalysts that are distinctly advantageous in optimizing the geometric/electronic effects and maximizing the metal atom utilization have attracted immense interest in the field of heterogeneous catalysis. However, the conventional impregnation techniques often cause poor dispersion of bimetallic particles even on high‐surface‐area supports owing to the lack of strong metal‐support interactions. Here, we present a general route to prepare Ru−M (M=Ga, In, Ge, Sn, Ni) bimetallic nanoclusters with average particle sizes of 1.02–1.24 nm by use of mesoporous sulfur‐doped carbon as supports. The strong chemical interaction between metal and the sulfur atoms that are doped in the carbon matrix can greatly suppress the aggregation of metal species during the H2‐reduction at 600 °C and thus guarantee the formation of small‐sized alloyed nanoclusters. Among these nanoclusters, the prepared bimetallic Ru−Sn nanocluster catalysts show enhanced catalytic activity for the selective hydrogenation of quinoline and furfural with a high turnover frequency of 2948 h−1 and 184 h−1, respectively.