100% selective cyclotrimerization of acetylene to benzene on Ag(111).

Benzene, a high-volume chemical, is produced from larger molecules by inefficient and environmentally harmful processes. Recent changes in hydrocarbon feedstocks from oil to gas motivate research into small molecule upgrading. For example, the cyclotrimerization of acetylene reaction has been demonstrated on Pd, Pd alloy, and Cu surfaces and catalysts, but they are not 100% selective to benzene. We discovered that acetylene can be converted to benzene with 100% selectivity on the Ag(111) surface. Our temperature programmed desorption experiments reveal a threshold acetylene surface coverage of ∼one monolayer, above which benzene is formed. Furthermore, additional layers of acetylene increase the amount of benzene produced while retaining 100% selectivity. Our scanning tunneling microscopy images show that acetylene prefers square packing on the Ag(111) surface at low coverages, which converts to hexagonal packing when acetylene multilayers are present. Within this denser layer, features consistent with the proposed C4 intermediates of the cyclotrimerization process are observed. Density functional theory calculations demonstrate that the barrier for forming the crucial C4 intermediate generally decreases as acetylene multilayers are formed because the multilayer interacts more strongly with the surface in the transition state than in the initial state. Given that acetylene desorbs from Ag(111) at ∼90 K, the C4 intermediate on the pathway to benzene must be formed below this temperature, implying that if Ag-based heterogeneous catalysts can be run at sufficiently high pressure and low enough temperature, efficient and selective trimerization of acetylene to benzene may be possible.

Observation and Characterization of Dicarbonyls on a RhCu Single-Atom Alloy.

Dicarbonyl species are ubiquitous on Rh/oxide catalysts and are known to form on Rh+ centers. However, dicarbonyl species have never been directly observed on single-atom alloys (SAAs) where the active site is metallic. Herein, using surface science and theoretical modeling, we provide evidence of dicarbonyl species at isolated Rh sites on a RhCu(100) SAA. This approach not only enables us to directly visualize dicarbonyl species at Rh sites but also demonstrates that the transition between the mono- and dicarbonyl configuration can be achieved by changing surface temperature and CO pressure. Density functional theory calculations further support the mono- and dicarbonyl assignments and provide evidence that these species should be stable on other SAA combinations. Together, these results provide a picture of the structure and energetics of both the mono- and dicarbonyl configurations on the RhCu(100) SAA surface and should aid with IR assignments on SAA nanoparticle catalysts.