In Situ Observations of UV-Induced Restructuring of Self-Assembled Porphyrin Monolayer on Liquid/Au(111) Interface at Molecular Level.

Porphyrin-derived molecules have received much attention for use in solar energy conversion devices, such as artificial leaves and dye-sensitized solar cells. Because of their technological importance, a molecular-level understanding of the mechanism for supramolecular structure formation in a liquid, as well as their stability under ultraviolet (UV) irradiation, is important. Here, we observed the self-assembled structure of free-base, copper(II), and nickel(II) octaethylporphyrin formed on Au(111) in a dodecane solution using scanning tunneling microscopy (STM). As evident in the STM images, the self-assembled monolayers (SAMs) of these three porphyrins on the Au(111) surface showed hexagonal close-packed structures when in dodecane solution. Under UV irradiation (λ = 365 nm), the porphyrin molecules in the SAM or the dodecane solution move extensively and form new porphyrin clusters on the Au sites that have a high degree of freedom. Consequently, the Au(111) surface was covered with disordered porphyrin clusters. However, we found that the porphyrin molecules decomposed under UV irradiation at 254 nm. Molecular-scale observation of the morphological evolution of the porphyrin SAM under UV irradiation can provide a fundamental understanding of the degradation processes of porphyrin-based energy conversion devices.

Thermal Evolution and Instability of CO-Induced Platinum Clusters on the Pt(557) Surface at Ambient Pressure.

Carbon monoxide (CO) is one of the most-studied molecules among the many modern industrial chemical reactions available. Following the Langmuir-Hinshelwood mechanism, CO conversion starts with adsorption on a catalyst surface, which is a crucially important stage in the kinetics of the catalytic reaction. Stepped surfaces show enhanced catalytic activity because they, by nature, have dense active sites. Recently, it was found that surface-sensitive adsorption of CO is strongly related to surface restructuring via roughening of a stepped surface. In this scanning tunneling microscopy study, we observed the thermal evolution of surface restructuring on a representative stepped platinum catalyst, Pt(557). CO adsorption at 1.4 mbar CO causes the formation of a broken-step morphology, as well as CO-induced triangular Pt clusters that exhibit a reversible disordered-ordered transition. Thermal instability of the CO-induced platinum clusters on the stepped surface was observed, which is associated with the reorganization of the repulsive CO-CO interactions at elevated temperature.

Work function engineering of SnO single crystal microplates with thermal annealing.

We synthesized black SnO single-crystal microplates via a sonochemical process and engineered the work function of the SnO microplates using thermal treatments. The as-synthesized SnO microplates have a wide (001) plane, as is clearly evident from TEM images and diffraction patterns. Surface potential measurements on the SnO microplates show that the work function changes as the annealing temperature increases. The TEM and XAS results after thermal treatments imply that the micro-sized SnO(001) single-crystals are stable up to about 400 °C in air, after which the surface starts to become locally oxidized. Consequently, the long-range ordering and lattice parameter of the SnO(001) single crystals started to change to make polycrystalline SnO2 at about 600 °C. These results demonstrate the ability to tune the work function of the microplates and suggest an intriguing way to engineer the electrical properties of nanostructures.

How Rh surface breaks CO2 molecules under ambient pressure.

Utilization of carbon dioxide (CO2) molecules leads to increased interest in the sustainable synthesis of methane (CH4) or methanol (CH3OH). The representative reaction intermediate consisting of a carbonyl or formate group determines yields of the fuel source during catalytic reactions. However, their selective initial surface reaction processes have been assumed without a fundamental understanding at the molecular level. Here, we report direct observations of spontaneous CO2 dissociation over the model rhodium (Rh) catalyst at 0.1 mbar CO2. The linear geometry of CO2 gas molecules turns into a chemically active bent-structure at the interface, which allows non-uniform charge transfers between chemisorbed CO2 and surface Rh atoms. By combining scanning tunneling microscopy, X-ray photoelectron spectroscopy at near-ambient pressure, and computational calculations, we reveal strong evidence for chemical bond cleavage of O‒CO* with ordered intermediates structure formation of (2 × 2)-CO on an atomically flat Rh(111) surface at room temperature.

Ambient-pressure atomic force microscope with variable pressure from ultra-high vacuum up to one bar.

We present the design and performance of an ambient-pressure atomic force microscope (AP-AFM) that allows AFM measurements using the laser deflection technique in a highly controlled environment from ultra-high vacuum (UHV) up to 1 bar with various gases. While the UHV of the AP-AFM system is obtained by a combination of turbo-molecular and ion pumps, for the higher-pressure studies, the ambient-pressure chamber is isolated from the pumps and high-purity gases are dosed via a leak valve from a gas manifold. The AP-AFM system, therefore, provides versatile AFM techniques, including the measurement of topography, friction and local conductance mapping, and force spectroscopy in a highly controlled environment with pressures ranging from UHV up to atmospheric pressure. Atomically resolved stick-slip images and force spectroscopy of highly ordered pyrolytic graphite (HOPG) at variable pressure conditions are presented to demonstrate the performance of the AP-AFM system. Force spectroscopy results of vacuum-cleaved HOPG, followed by exposure to lab air, oxygen, and methane show that adhesion between the AFM tip and the HOPG depends significantly on the exposed gas and pressure. Our results show that the deposition of airborne hydrocarbon impurities at ambient conditions leads to a significant change in adhesion force, implying that the wettability of the HOPG surface depends on the environment and the pressure.

Effect of the metal-support interaction on the activity and selectivity of methanol oxidation over Au supported on mesoporous oxides.

To elucidate the factors affecting the catalytic properties of supported Au catalysts on the metal oxide support we investigated Au NPs deposited on crystallized mesoporous transition-metal oxides (m-oxides: Co3O4, NiO, and α-Fe2O3) prepared using the nanocasting method. The metal-oxide interaction in Au/mesoporous oxides resulted in higher catalytic activity for converting methanol to CO2 as a full oxidation product than pure m-oxides. Au/m-Fe2O3 exhibited high activity and low selectivity for methyl formate as a partial oxidative coupling product. We correlate the change in activity and selectivity with the interface between the Au and m-oxides.

Plasmonic hot carrier-driven oxygen evolution reaction on Au nanoparticles/TiO2 nanotube arrays.

The use of hot carriers generated from the decay of localized surface plasmon resonance in noble metal nanoparticles is a promising concept for photocatalysis. Here, we report the enhancement of photocatalytic activity by the flow of hot electrons on TiO2 nanotube arrays decorated with 5-30 nm Au nanoparticles as photoanodes for photoelectrochemical water splitting. This enhanced photocatalytic activity is correlated to the size of the Au nanoparticles, where higher oxygen evolution was observed on the smaller nanoparticles. Conductive atomic force microscopy and ultraviolet photoelectron spectroscopy were used to characterize the Schottky barrier between Au and TiO2, which reveals a reduction in the Schottky barrier with the smaller Au nanoparticles and produces an enhanced transfer of photoinduced hot carriers. This study confirms that the higher photocatalytic activity was indeed driven by the hot electron flux generated from the decay of localized surface plasmon resonance.

Adsorbate-driven reactive interfacial Pt-NiO1-x nanostructure formation on the Pt3Ni(111) alloy surface.

The origin of the synergistic catalytic effect between metal catalysts and reducible oxides has been debated for decades. Clarification of this effect, namely, the strong metal-support interaction (SMSI), requires an understanding of the geometric and electronic structures of metal-metal oxide interfaces under operando conditions. We show that the inherent lattice mismatch of bimetallic materials selectively creates surface segregation of subsurface metal atoms. Interfacial metal-metal oxide nanostructures are then formed under chemical reaction environments at ambient pressure, which thus increases the catalytic activity for the CO oxidation reaction. Our in situ surface characterizations using ambient-pressure scanning tunneling microscopy and ambient-pressure x-ray photoelectron spectroscopy exhibit (i) a Pt-skin layer on the Pt-Ni alloyed surface under ultrahigh vacuum, (ii) selective Ni segregation followed by the formation of NiO1-x clusters under oxygen gas, and (iii) the coexistence of NiO1-x clusters on the Pt-skin during the CO oxidation reaction. The formation of interfacial Pt-NiO1-x nanostructures is responsible for a highly efficient step in the CO oxidation reaction. Density functional theory calculations of the Pt3Ni(111) surface demonstrate that a CO molecule adsorbed on an exposed Pt atom with an interfacial oxygen from a segregated NiO1-x cluster has a low surface energy barrier of 0.37 eV, compared with 0.86 eV for the Pt(111) surface.

Charge transport-driven selective oxidation of graphene.

Due to the tunability of the physical, electrical, and optical characteristics of graphene, precisely controlling graphene oxidation is of great importance for potential applications of graphene-based electronics. Here, we demonstrate a facile and precise way for graphene oxidation controlled by photoexcited charge transfer depending on the substrate and bias voltage. It is observed that graphene on TiO2 is easily oxidized under UV-ozone treatment, while graphene on SiO2 remains unchanged. The mechanism for the selective oxidation of graphene on TiO2 is associated with charge transfer from the TiO2 to the graphene. Raman spectra were used to investigate the graphene following applied bias voltages on the graphene/TiO2 diode under UV-ozone exposure. We found that under a reverse bias of 0.6 V on the graphene/TiO2 diode, graphene oxidation was accelerated under UV-ozone exposure, thus confirming the role of charge transfer between the graphene and the TiO2 that results in the selective oxidation of the graphene. The selective oxidation of graphene can be utilized for the precise, nanoscale patterning of the graphene oxide and locally patterned chemical doping, finally leading to the feasibility and expansion of a variety of graphene-based applications.

A highly N-doped carbon phase "dressing" of macroscopic supports for catalytic applications.

The straightforward "dressing" of macroscopically shaped supports (i.e.ß-SiC and α-Al2O3) with a mesoporous and highly nitrogen-doped carbon-phase starting from food-processing raw materials is described. The as-prepared composites serve as highly efficient and selective metal-free catalysts for promoting industrial key-processes at the heart of renewable energy technology and environmental protection.

Single-Layer Graphene as an Effective Mediator of the Metal-Support Interaction.

Single-layer chemical vapor deposition (CVD)-grown graphene was transferred onto a ZnO (0001) substrate forming a large-area, low-defect density, protective layer. The quality of the graphene layer and its effect on the interaction between the ZnO support and vapor-deposited cobalt particles was investigated by spectroscopic and microscopic techniques. We demonstrate that the in-between graphene layer influences both the oxidation state and the morphology of cobalt upon annealing in vacuum. In particular, cobalt strongly interacts with the bare ZnO substrate forming flat particles, which are readily oxidized and redispersed upon annealing in ultrahigh vacuum conditions. In contrast, in the presence of the graphene interlayer, cobalt forms highly dispersed nanoparticles, which are resistant to oxidation, but prone to surface diffusion and agglomeration. The graphene layer exhibits remarkable stability upon cobalt deposition and vacuum annealing, while interaction with reactive gases can facilitate the formation of defects.