Understanding how molecules can restructure the surfaces of heterogeneous catalysts under reaction conditions requires methods that can visualize atoms in real space and time. We applied a newly developed aberration-corrected environmental transmission electron microscopy to show that adsorbed carbon monoxide (CO) molecules caused the {100} facets of a gold nanoparticle to reconstruct during CO oxidation at room temperature. The CO molecules adsorbed at the on-top sites of gold atoms in the reconstructed surface, and the energetic favorability of this reconstructed structure was confirmed by ab initio calculations and image simulations. This atomic-scale visualizing method can be applied to help elucidate reaction mechanisms in heterogeneous catalysis.

The single Pt 1 and Au 1 atoms stabilized by lattice oxygen on ZnO{1010} surface for methanol steam reforming is reported. Density functional theory calculations reveal that the catalysis of the single precious metal atoms together with coordinated lattice oxygen stems from its stronger binding toward the intermediates, lowering reaction barriers, changing on the reaction pathway, enhancing greatly the activity. The measured turnover frequency of single Pt 1 sites was more than 1000 times higher than the pristine ZnO. The results provide valuable insights for the catalysis of the atomically dispersed precious metals on oxide supports.

Synergistic effects have been discussed extensively in bimetallic heterogeneous catalysis, but it remains unclear how the effects function at the atomic scale. Here, we report a dual single-atom catalyst (DSAC) Ir1Mo1/TiO2 displaying much greater catalytic chemoselectivity (>96%, at 100% conversion) than comparable single-atom catalysts (SACs) Ir1/TiO2 (38%, at 87% conversion) and Mo1/TiO2 (no activity) for the hydrogenation of 4-nitrostyrene (4-NS) to 4-vinylaniline (4-VA). Activation of the TiO2-supported bimetallic carbonyl cluster Ir2Mo2(CO)10(η5-C5H5)2 in an Ar atmosphere affords the DSAC Ir1Mo1/TiO2. Characterization of the dual single-atom structure confirms that it consists of well-dispersed Ir single atoms (Ir1) and Mo single atoms (Mo1) on TiO2. Density functional theory studies reveal that Ir1 sites effect H2 activation while Mo1 sites are responsible for 4-NS adsorption, with synergistic cooperation between the two sets of single atoms contributing to the better catalytic performance for the hydrogenation of 4-NS. This work provides a deep understanding of synergistic effects in dual single-atom catalysis.

The stoichiometric single-and bilayer ZnO(0001) have been prepared by reactive deposition of Zn on Au(111) and studied in detail with X-ray photoelectron spectroscopy, scanning tunneling microscopy, and density functional theory calculations. Both single-and bilayer ZnO(0001) adopt a planar, graphite-like structure similar to freestanding ZnO(0001) due to the weak van der Waals interactions dominating their adhesion with the Au(111) substrate. At higher temperature, the single-layer ZnO(0001) converts gradually to bilayer ZnO(0001) due to the twice stronger interaction between two ZnO layers than the interfacial adhesion of ZnO with Au substrate. It is found that Cu atoms on the surface of bilayer ZnO(0001) are mobile with a diffusion barrier of 0.31 eV and likely to agglomerate and form nanosized particles at low coverages; while Cu atoms tend to penetrate a single layer of ZnO(0001) with a barrier of 0.10 eV, resulting in a Cu free surface.