Takanori Koitaya, Susumu Yamamoto, Iwao Matsuda, Jun Yoshinobu
In-situ analysis of heterogeneous catalysts under reaction condition is indispensable to understand reaction mechanisms and nature of active sites. Ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) is one of the powerful methods to investigate chemical states of catalysts and reaction intermediates adsorbed on the surface. In this review, reaction of carbon dioxide on Cu(997) and Zn-deposited Cu(997) surfaces are discussed as an example of surface chemistry of weakly adsorbed molecules, together with a brief overview of recent progress in AP-XPS methods.
Surface X-ray diffraction is a powerful tool for studying the atomic structure of buried interfaces nondestructively. The analysis is often limited to the static structures, since the acquisition of crystal truncation rod (CTR) profile dataset is lengthy. Recently, high-speed methods have been developed by several groups, aiming for the in operando study of interface phenomena. Our method uses energy-dispersive convergent X-rays and area detector, and allows the quantitative structure analysis during irreversible phenomena in a typical time frame of 1 s. In this review, the energy-dispersive method is compared with the other high-speed methods which use high-energy X-rays with a grazing incidence geometry and transmission geometry, and then two examples of the real-time monitoring are presented, the photo-induced wettability transition of the rutile-TiO2(110) surface and an electrochemical reaction on the Pt(111) electrode surface, to show the capability of the energy-dispersive method.
Establishing an accurate view of the photocatalytic mechanism of titanium dioxide (TiO2) has been a challenging task since the discovery of the Honda-Fujishima effect. Despite the great success of catalytic studies in elucidating the chemical and physical aspects of photocatalysis, many questions remain. A surface science approach, which is characterized by the use of atomically well-defined surfaces in precisely controlled environments, is a powerful tool to shed light on the fundamental mechanism, especially the dynamics of photoexcited carriers. In the present contribution, recent progress in photocatalytic research that correlates photocatalytic activity and carrier dynamics on rutile and anatase TiO2 is reviewed. A special focus is placed on the lifetime of photoexcited carriers. We present a method to determine the carrier lifetime; pump-probe time-resolved soft X-ray photoelectron spectroscopy, utilizing an ultraviolet laser as a pump light and a synchrotron radiation as a probe light. The carrier lifetime is found to be linearly correlated with the photocatalytic decomposition/desorption rate of acetic acid adsorbed on single-crystal TiO2 surfaces. The important role of a potential barrier on the TiO2 surface, which influences the carrier lifetime and the photocatalytic activity, is discussed.
Raman spectroscopy provides a meaningful fingerprint for sensing and discriminating materials, and surface-enhanced Raman scattering (SERS) can dramatically increase Raman signals up to the single-molecule level of sensitivity. Graphene, a monolayer carbon sheet, has recently attracted considerable attention as a unique SERS substrate. However, there are various types of graphene materials, and the SERS application category is significantly correlated to the structure and quality of the graphene. This review provides a broad perspective on this research area, intended for researchers of diverse fields. First, we categorize the graphene-based SERS applications based on their structure. Second, we introduce the types of graphene (graphene oxide, reduced graphene oxide, chemical vapor deposited graphene, and carbon nanowalls) and their synthesis methods. Thereafter, we highlight state-of-the-art studies for each category of graphene-based SERS.
Alfred J. Weymouth, Daniel Wastl, Franz J. Giessibl
It's hard to imagine that we can take a splinter and sharpen it down to the atomic level. It's even more impressive that we can bring this sharp tip close to a surface, scan it over the surface, and be sensitive to the tiny forces between the apex atom and individual atoms on the surface. Measuring and interpreting these forces is the goal of high-resolution atomic force microscopy (AFM). We perform frequency-modulation AFM (FM-AFM), in which we oscillate the tip and record the change in frequency as a measure of the interaction with the surface. FM-AFM performed in vacuum with stiff sensors has lead to amazing discoveries. Now, we are returning to the challenge of imaging samples in device- and biologically-relevant conditions. This contribution summarizes work that was performed in the Giessibl group to image with atomic resolution in ambient and liquid environments. We demonstrated atomic resolution with the qPlus sensor on KBr, and followed this with investigations on graphitic surfaces. We have also shown single-atomic defects and steps on the calcite surface. [DOI: 10.1380/ejssnt.2018.351]
Theodore L. Einstein, Ludwig Bartels, Josue R. Morales-Cifuentes
This paper modestly expands an invited talk at ISSS-8 with the same title. After reviewing the relevant interactions between adsorbates on substrates with metallic surface states [especially Cu(111)], it focuses on organic adsorbates. Of particular interest are those which form honeycomb lattices with pores of various sizes. The nature of the confined states derived from the surface-state electrons is discussed as their effect on admolecules inside the pores. [DOI: 10.1380/ejssnt.2018.201]
The electron spin governs many phenomena in modern condensed matter physics, such as magnetism, superconductivity, etc. Often, minute details in the electronic structure determine the physical behavior of a material. Photoelectron emission—being the most established approach to explore electronic structures—is currently entering a new era thanks to a breathtaking development in light sources, spectrometer concepts, and spin detectors. In particular, the evolution in novel highly efficient electron spin polarimeters opens up new experimental opportunities and permits unequaled insights into the electronic structure. This contribution will discuss several examples in this field of spin-dependent interactions and spin-based phenomena. A prominent one refers to the class of topological insulators, where strong spin-orbit coupling (SOC) causes a unique spin-momentum locking around the Dirac cone. Transition metal dichalcogenides consist of quasi-2D layers coupled by v. d. Waals interactions. Here, strong SOC leads to pronounced hybridization effects. We also address fundamental issues in ferromagnetism, e.g., the complex interplay of SOC and exchange interaction, causing characteristic k-, spin- and symmetry-dependent band mixing. Using spin- and time-resolved photoemission we explore ultrafast spin dynamics in ferromagnets driven by strong ultrashort laser pulses. We find the changes in both majority and minority spin states to take place on a 100 fs time scale and to be compatible with band mirroring. In this contribution, we will discuss several new aspects of spin-dependent and spin-resolved photoemission covering both static and dynamic issues of electronic states. [DOI: 10.1380/ejssnt.2018.177]