Unraveling the Dynamic Processes of Methanol Electrooxidation at Isolated Rhodium Sites by In Situ Electrochemical Scanning Tunneling Microscopy

Materials with isolated single-atom Rh–N4 sites are emerging as promising and compelling catalysts for methanol electrooxidation. Herein, we carried out an in situ electrochemical scanning tunneling microscopy (ECSTM) investigation of the dynamic processes of methanol absorption and catalytic conversion in the rhodium octaethylporphyrin (RhOEP)-catalyzed methanol oxidation reaction at the molecular scale. The high-contrast RhOEP-CH3OH complex formed by methanol adsorption was visualized distinctly in the STM images. The Rh–C adsorption configuration of methanol on isolated rhodium sites was identified on the basis of a series of control experiments and theoretical simulation. The adsorption energy of methanol on RhOEP was obtained from quantitative analysis. In situ ECSTM experiments present an explicit description of the transformation of the intermediate species in the catalytic process. By qualitatively evaluating the rate constants of different stages in the reaction at the microscopic level, we considered the CO transformation/desorption as the critical step for determining the reaction dynamics. Methanol adsorption was found to be correlated with RhOEP oxidation in the initial stage of the reaction, and the dynamic information was revealed unambiguously by in situ potential step experiments. This work provides microscopic results for the catalytic mechanism of Rh–N4 sites for methanol electrooxidation, which is instructive for the rational design of the high-performance catalyst

Palladium-Catalyzed Radical Cascade Iododifluoromethylation/Cyclization of 1,6-Enynes with Ethyl Difluoroiodoacetate

A novel and convenient Pd-catalyzed radical cascade iododifluoromethylation/cyclization of 1,6-enynes with ethyl difluoroiodoacetate is demonstrated. The proposed transformation presents high stereoselectivity under mild and facile reaction conditions, thereby allowing an efficient access to a variety of iodine-containing difluoromethylated pyrrolidines. A possible radical pathway for the transformation is proposed on the basis of the results of control experiments and relevant literature reviews

Ruthenium-Catalyzed Direct C–H Amidation of Arenes: A Mechanistic Study

We report mechanistic studies of C–H activitation/amidation reactions using azides as the amino source catalyzed by [RuCl₂(<i>p</i>-cymene)]₂. We have achieved two intermediates in the catalytic cycle (C₅H₄NC₆H₄)­Ru­(<i>p</i>-cymene)Cl and (C₅H₄NC₆H₄)­NArRu­(<i>p</i>-cymene)Cl (Ar = NO₂C₆H₄SO₂). Furthermore, the process from (C₅H₄NC₆H₄)­Ru­(<i>p</i>-cymene)Cl to (C₅H₄NC₆H₄)­NArRu­(<i>p</i>-cymene)Cl was monitored by ¹⁹F NMR and a ruthenium–imido species was proposed to explain the formation of the azacyclopropane analogue

Silver Surface-Assisted Dehydrobrominative Cross-Coupling between Identical Aryl Bromides

Cross-coupling reactions represent an indispensable tool in chemical synthesis. An intriguing challenge in this field is to achieve selective cross-coupling between two precursors with similar reactivity or, to the limit, the identical molecules. Here we report an unexpected dehydrobrominative cross-coupling between 1,3,5-tris(2-bromophenyl)benzene molecules on silver surfaces. Using scanning tunneling microscopy, we examine the reaction process at the single-molecular level, quantify the selectivity of the dehydrobrominative cross-coupling, and reveal the modulation of selectivity by substrate lattice-related catalytic activity or molecular assembly effect. Theoretical calculations indicate that the dehydrobrominative cross-coupling proceeds via regioselective C–H bond activation of debrominated TBPB and subsequent highly selective C–C coupling of the radical-based intermediates. The reaction kinetics plays an important role in the selectivity for the cross-coupling. This work not only expands the toolbox for chemical synthesis but also provides important mechanistic insights into the selectivity of coupling reactions on the surface

Two-Dimensional Transition Metal Honeycomb Realized: Hf on Ir(111)

Two-dimensional (2D) honeycomb systems made of elements with d electrons are rare. Here, we report the fabrication of a transition metal (TM) 2D layer, namely, hafnium crystalline layers on Ir(111). Experimental characterization reveals that the Hf layer has its own honeycomb lattice, morphologically identical to graphene. First-principles calculations provide evidence for directional bonding between adjacent Hf atoms, analogous to carbon atoms in graphene. Calculations further suggest that the freestanding Hf honeycomb could be ferromagnetic with magnetic moment μ/Hf = 1.46 μ_B. The realization and investigation of TM honeycomb layers extend the scope of 2D structures and could bring about novel properties for technological applications

Epitaxial Growth of Flat Antimonene Monolayer: A New Honeycomb Analogue of Graphene

Group-V elemental monolayers were recently predicted to exhibit exotic physical properties such as nontrivial topological properties, or a quantum anomalous Hall effect, which would make them very suitable for applications in next-generation electronic devices. The free-standing group-V monolayer materials usually have a buckled honeycomb form, in contrast with the flat graphene monolayer. Here, we report epitaxial growth of atomically thin flat honeycomb monolayer of group-V element antimony on a Ag(111) substrate. Combined study of experiments and theoretical calculations verify the formation of a uniform and single-crystalline antimonene monolayer without atomic wrinkles, as a new honeycomb analogue of graphene monolayer. Directional bonding between adjacent Sb atoms and weak antimonene-substrate interaction are confirmed. The realization and investigation of flat antimonene honeycombs extends the scope of two-dimensional atomically-thick structures and provides a promising way to tune topological properties for future technological applications

Monolayer PtSe₂, a New Semiconducting Transition-Metal-Dichalcogenide, Epitaxially Grown by Direct Selenization of Pt

Single-layer transition-metal dichalcogenides (TMDs) receive significant attention due to their intriguing physical properties for both fundamental research and potential applications in electronics, optoelectronics, spintronics, catalysis, and so on. Here, we demonstrate the epitaxial growth of high-quality single-crystal, monolayer platinum diselenide (PtSe₂), a new member of the layered TMDs family, by a single step of direct selenization of a Pt(111) substrate. A combination of atomic-resolution experimental characterizations and first-principle theoretic calculations reveals the atomic structure of the monolayer PtSe₂/Pt­(111). Angle-resolved photoemission spectroscopy measurements confirm for the first time the semiconducting electronic structure of monolayer PtSe₂ (in contrast to its semimetallic bulk counterpart). The photocatalytic activity of monolayer PtSe₂ film is evaluated by a methylene-blue photodegradation experiment, demonstrating its practical application as a promising photocatalyst. Moreover, circular polarization calculations predict that monolayer PtSe₂ has also potential applications in valleytronics