Adsorption of acrolein and its hydrogenation products on Cu(111).

The adsorption of acrolein and its hydrogenation products propanal, 1-propanol, and 2-propenol on Cu(111) was studied by reflection absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD). The experimental RAIR spectra were obtained by adsorbing multilayers of each molecule at 85 K and then annealing the surface up to 200 K to desorb the multilayer and produce the most stable monolayer structure on the surface. Each of the four molecules adsorbs weakly to the surface and desorbs at temperatures below 225 K.

Dissociation of Single O Molecules on Ag(110) by Electrons, Holes, and Localized Surface Plasmons.

A detailed understanding of the dissociation of O molecules on metal surfaces induced by various excitation sources, electrons/holes, light, and localized surface plasmons, is crucial not only for controlling the reactivity of oxidation reactions but also for developing various oxidation catalysts. The necessity of mechanistic studies at the single-molecule level is increasingly important for understanding interfacial interactions between O molecules and metal surfaces and to improve the reaction efficiency. We review single-molecule studies of O dissociation on Ag(110) induced by various excitation sources using a scanning tunneling microscope (STM).

Dissociation Mechanism of a Single O Molecule Chemisorbed on Ag(110).

The dissociation of O molecules chemisorbed on silver surfaces is an essential reaction in industry, and the dissociation mechanism has long attracted attention. The detailed dissociation mechanism was studied at the single-molecule level on Ag(110) by using a scanning tunneling microscope (STM). The dissociation reaction was found to be predominantly triggered by inelastically tunneled holes from the STM tip due to the significantly distributed density of states below the Fermi level of the substrate.

The influence of palladium on the hydrogenation of acetylene on Ag(111).

We have used reflection absorption infrared spectroscopy (RAIRS) and temperature programmed reaction (TPR) to study the selective hydrogenation of acetylene on both a clean Ag(111) surface and on a Pd/Ag(111) single-atom-alloy surface. The partial hydrogenation of acetylene to ethylene is an important catalytic process that is often carried out using PdAg alloys. It is challenging to study the reaction with ultrahigh vacuum techniques because H does not dissociate on Ag(111), and while H will dissociate at Pd sites, H-atom spillover from Pd to Ag sites does not generally occur.

Post-COVID-19 Syndrome (Long Haul Syndrome): Description of a Multidisciplinary Clinic at Mayo Clinic and Characteristics of the Initial Patient Cohort.

Objective: To describe characteristics of a series of patients reporting prolonged symptoms after an infection with coronavirus disease 2019 (COVID-19).

Patients And Methods: This study describes the multidisciplinary COVID-19 Activity Rehabilitation Program, established at Mayo Clinic to evaluate and treat patients with post-COVID syndrome, and reports the clinical characteristics of the first 100 patients receiving evaluation and management during the timeframe of June 1, 2020, and December 31, 2020.

Results: The cohort consisted of 100 patients (mean age, 45.

Interaction of CO with Pt nanoclusters on a graphene-covered Ru(0001) surface.

The adsorption of CO on Pt nanoclusters on a single layer of graphene epitaxially grown on the Ru(0001) surface [Gr/Ru(0001)] was studied with reflection absorption infrared spectroscopy (RAIRS) and temperature programmed desorption (TPD). The graphene layer was grown through exposure to ethylene using a method that has previously been shown to completely cover the surface. As CO adsorbs on Ru(0001) but not on graphene, the complete coverage of the Ru(0001) surface by graphene was verified with TPD as no CO adsorption was detectable.

Adsorption properties of acrolein, propanal, 2-propenol, and 1-propanol on Ag(111).

Reflection absorption infrared spectroscopy and temperature programmed desorption were used to study the adsorption of acrolein, its partial hydrogenation products, propanal and 2-propenol, and its full hydrogenation product, 1-propanol on the Ag(111) surface. Each molecule adsorbs weakly to the surface and desorbs without reaction at temperatures below 220 K. For acrolein, the out-of plane bending modes are more intense than the C[double bond, length as m-dash]O stretch at all coverages, indicating that the molecular plane is mainly parallel to the surface.

Single-Molecule Study of a Plasmon-Induced Reaction for a Strongly Chemisorbed Molecule.

Chemical reactions induced by plasmons achieve effective solar-to-chemical energy conversion. However, the mechanism of these reactions, which generate a strong electric field, hot carriers, and heat through the excitation and decay processes, is still controversial. In addition, it is not fully understood which factor governs the mechanism.

Reaction pathways for HCN on transition metal surfaces.

The adsorption and decomposition of HCN on the Pd(111) and Ru(001) surfaces have been studied with reflection absorption infrared spectroscopy and density functional theory calculations. The results are compared to earlier studies of HCN adsorption on the Pt(111) and Cu(100) surfaces. In all cases the initial adsorption at low temperatures gives rise to a ν(C-H) stretch peak at ∼3300 cm-1, which is very close to the gas phase value indicating that the triple CN bond is retained for the adsorbed molecule.

Real-space and real-time observation of a plasmon-induced chemical reaction of a single molecule.

Plasmon-induced chemical reactions of molecules adsorbed on metal nanostructures are attracting increased attention for photocatalytic reactions. However, the mechanism remains controversial because of the difficulty of direct observation of the chemical reactions in the plasmonic field, which is strongly localized near the metal surface. We used a scanning tunneling microscope (STM) to achieve real-space and real-time observation of a plasmon-induced chemical reaction at the single-molecule level.

Growth of Pd Nanoclusters on Single-Layer Graphene on Cu(111).

We report scanning tunneling microscopy results on the nucleation and growth of Pd nanoclusters on a single layer of graphene on the Cu(111) surface. The shape, organization, and structural evolution of the Pd nanoclusters were investigated using two different growth methods, continuous and stepwise. The size and shape of the formed nanoclusters were found to greatly depend on the growth technique used.

Surface chemistry of propanal, 2-propenol, and 1-propanol on Ru(001).

Adsorption and thermal chemistry of propanal, 2-propenol, and 1-propanol on Ru(001) were studied using temperature programmed reaction spectroscopy (TPRS) and reflection absorption infrared spectroscopy (RAIRS). The results show that each molecule adsorbs molecularly at 90 K and displays the same spectral features as observed for the corresponding liquids after 1.0 L exposures.

Direct Pathway to Molecular Photodissociation on Metal Surfaces Using Visible Light.

We demonstrate molecular photodissociation on single-crystalline metal substrates, driven by visible-light irradiation. The visible-light-induced photodissociation on metal substrates has long been thought to never occur, either because visible-light energy is much smaller than the optical energy gap between the frontier electronic states of the molecule or because the molecular excited states have short lifetimes due to the strong hybridization between the adsorbate molecular orbitals (MOs) and metal substrate. The S-S bond in dimethyl disulfide adsorbed on both Cu(111) and Ag(111) surfaces was dissociated through direct electronic excitation from the HOMO-derived MO (the nonbonding lone-pair type orbitals on the S atoms (n)) to the LUMO-derived MO (the antibonding orbital localized on the S-S bond (σ*)) by irradiation with visible light.

Single-Molecule Dynamics in the Presence of Strong Intermolecular Interactions.

In contrast to conventional spectroscopic studies of adsorbates at high coverage that provide only spatially averaged information, we have characterized the laterally confined shuttling dynamics of a single molecule under the influence of intermolecular interactions by vibrational spectroscopy using a scanning tunneling microscope. The bridge sites on Pt(111) are only occupied by a CO molecule that is surrounded by four other CO molecules at on-top sites. The bridge-site CO undergoes laterally confined shuttling toward an adjacent on-top site to transiently occupy a metastable site, which is slightly displaced from the center of an on-top site through repulsive interaction with adjacent on-top CO molecules.

Atomic-Scale Dynamics of Surface-Catalyzed Hydrogenation/Dehydrogenation: NH on Pt(111).

Low-temperature scanning tunneling microscopy (LT-STM) was used to move hydrogen atoms and dissociate NH molecules on a Pt(111) surface covered with an ordered array of nitrogen atoms in a (2 × 2) structure. The N-covered Pt(111) surface was prepared by ammonia oxydehydrogenation, which was achieved by annealing an ammonia-oxygen overlayer to 400 K. Exposing the N-covered surface to H2(g) forms H atoms and NH molecules.

Surface hydrogenation reactions at the single-molecule level.

Hydrogenation and dehydrogenation reactions on metal surfaces are among the most important in heterogeneous catalysis. Such reactions can be observed and characterized at the single-molecule level with low temperature scanning tunnelling microscopy (LT-STM). A brief review of such studies is presented.

Surface morphology of atomic nitrogen on Pt(111).

The surface morphology of chemisorbed N on the Pt(111) surface has been studied at the atomic level with low temperature scanning tunneling microscopy (STM). When N is coadsorbed with O on the surface, they form a mixed (2 × 2)-N+O structure. When the surface is covered with N atoms only, isolated atoms and incomplete (2 × 2) patches are observed at low coverages.

Observation of Tunneling in the Hydrogenation of Atomic Nitrogen on the Ru(001) Surface to Form NH.

The kinetics of NH and ND formation and dissociation reactions on Ru(001) were studied using time-dependent reflection absorption infrared spectroscopy (RAIRS). Our results indicate that NH and ND formation and dissociation on Ru(001) follow first-order kinetics. In our reaction temperature range (320-390 K for NH and 340-390 K for ND), the apparent activation energies for NH and ND formation were found to be 72.

Molecular Oxygen Network as a Template for Adsorption of Ammonia on Pt(111).

Low-temperature scanning tunneling microscopy (STM) was used to observe a mixed NH3-O2 overlayer on Pt(111). At adsorption temperatures below 50 K, the chemisorbed O2 molecules form an ordered network at high coverages. The STM images reveal that this network features a distributed set of holes corresponding to on-top sites of the Pt lattice that are surrounded by two or three O2 molecules.

Orbital-selective single molecule reactions on a metal surface studied using low-temperature scanning tunneling microscopy.

The injection of tunneling electrons from the scanning tunneling microscope tip into the molecule induces the single molecule reactions of acetonitrile adsorbed on Pt(111). The voltage dependence indicated that the resonant tunneling of electrons into the antibonding molecular orbitals gives rise to the desorption and the decomposition of acetonitrile.

Surface science studies of metal hexaborides.

Over 30 years of surface science research on metal hexaborides are reviewed. Of this class of compounds, lanthanum hexaboride has been the subject of the majority of the studies because of its outstanding properties as a thermionic emitter. The use of LaB cathodes as an electron source stems from the unusually low work function of ∼2.

Thermal and electron-induced decomposition of 2-butanol on Pt(111).

The adsorption, thermal evolution, and electron irradiation of 2-butanol on Pt(111) were investigated with reflection absorption infrared spectroscopy (RAIRS). A simulated vibrational spectrum of a single 2-butanol molecule was calculated using density functional theory to facilitate vibrational assignments. Exposures of 0.

Synthesis and characterization of single-crystal strontium hexaboride nanowires.

Catalyst-assisted growth of single-crystal strontium hexaboride (SrB6) nanowires was achieved by pyrolysis of diborane (B2H6) over SrO powders at 760-800 degrees C and 400 mTorr in a quartz tube furnace. Raman spectra demonstrate that the nanowires are SrB6, and transmission electron microscopy along with selected area diffraction indicate that the nanowires consist of single crystals with a preferred [001] growth direction. Electron energy loss data combined with the TEM images indicate that the nanowires consist of crystalline SrB 6 cores with a thin (1 to 2 nm) amorphous oxide shell.

Reversible control of hydrogenation of a single molecule.

Low-temperature scanning tunneling microscopy was used to selectively break the N-H bond of a methylaminocarbyne (CNHCH3) molecule on a Pt(111) surface at 4.7 kelvin, leaving the C-H bonds intact, to form an adsorbed methylisocyanide molecule (CNCH3). The methylisocyanide product was identified through comparison of its vibrational spectrum with that of directly adsorbed methylisocyanide as measured with inelastic electron tunneling spectroscopy.