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Single-atoms (SAs) with atomically coordinated reaction centers are considered the next generation of catalysts that can exhibit exceptional catalytic efficiency. However, the general concern about thermodynamic vulnerabilities of SAs questions their practical value. Moreover, whether the inherent catalytic nature of SAs is superior compared with that of larger nanoparticles is still under debate. Here, we address two controversies by a comparative study using two catalysts: Pt/TiO2 and Pt/CeOx-TiO2. Based on a hierarchical study of density functional theory, time-resolved catalysis performance test, in situ infrared spectroscopy, and operando X-ray absorption spectroscopy, we could unveil the catalytic nature of Pt-SAs and their stability. By utilizing the heterogeneous interface formed between TiO2 supporting particles and CeOx clusters formed on the surface of TiO2, we preferentially synthesized Pt-SAs pinned at the CeOx-TiO2 interfaces on CeOx-TiO2 hybrid-oxide supports. The strong electronic coupling between the Pt-SAs and the Ce ions at the CeOx-TiO2 interfaces enhanced the catalytic activity toward CO oxidation of Pt-SAs and improved the long-term stability under CO oxidation conditions. The CO oxidation activity of Pt-SAs stabilized at CeOx-TiO2 was improved by 13.5 times at 200 °C compared with the Pt-SAs on TiO2. The results present how to easily improve the activity and stability of Pt-SAs using a simple interface control method. Moreover, we demonstrate that the catalytic activity and the stability of Pt-SAs can be monitored through the chemical state of the interfaces. Our study provides comprehensive understanding about the catalytic nature as well as a novel strategy toward applications of Pt-SAs, enabling sustainable use of Pt in heterogeneous catalysts.

Despite extensive research on utilizing plasmonic hot carriers to advance photovoltaics and photocatalysts, achieving high hot‐carrier flux remains challenging due to their rapid relaxation. Recent studies have shown that combining plasmonic metals with perovskites improves hot‐electron flow, due to the slow hot‐electron relaxation in perovskites. Additionally, perovskites offer the advantage of facile bandgap tuning through composition changes. Herein, the influence of tuning the perovskite bandgap on the lifetime and flow of hot electrons in a perovskite/plasmonic Au/TiO2 nanodiode is explored. The findings reveal that perovskites with wider bandgaps exhibit improved hot‐electron lifetime and flow, attributed to the modified hot‐electron energy favoring a slower energy loss rate, as verified by ultrafast transient absorption spectroscopic analysis. It is believed that the results successfully demonstrate the integration of engineered hot‐carrier physics into device functions, providing valuable guidance for the design of optimized hot‐carrier‐based devices in the future. [ABSTRACT FROM AUTHOR]

Polymer-based triboelectric nanogenerators (TENGs) have held promise due to their excellent interfacial conformity and ease of fabrication. However, the role of surface roughness in triboelectricity requires further study. In this study, we have manipulated the nano-/micro-scale roughness configuration in polydimethylsiloxane (PDMS) over a wide range of extents using various sandpaper-based templates. According to the power spectral density analysis, the spatial frequency of template-free PDMS exhibits several distinct bandwidth regions each with different fractal dimensions significantly higher than 2, despite having the lowest roughness value. In contrast, most template-based PDMS shows an entire spatial frequency region that scales nearly with a single power factor corresponding to a fractal dimension as low as 2, despite slight increases in roughness values. Consequently, the surface temperature gradient and output performance of TENG increased, following the trend of fractal dimension and roughness, but the surface potentials have remained almost invariant. However, excessive increases in the surface roughness cause the spatial frequency to be divided once again into several different bandwidth regions with different cutoffs and higher fractal dimensions. These results suggest that the performance of TENG can be controlled by tuning both surface roughness and self-affine properties over multiple scales. Specifically, adhesive interaction becomes dominant on surfaces with lower fractality, enhancing TENG performance due to the expanded contact area. This study sheds light on the relationship among triboelectricity, thermal dissipation, and topography. [ABSTRACT FROM AUTHOR]

The lubricating properties of water have been discussed extensively for millennia. Water films can exhibit wearless high friction in the form of cold ice, or act as lubricants in skating and skiing when a liquid. At the fundamental level, friction is the result of a balance between the rate of energy generation by phonon excitation during sliding and drainage of the energy from the interface by coupling with bulk atoms. Using atomic force microscopy, we found that when H2O intercalates between graphene and mica, it increases the friction between the tip and the substrate, dependent on the thickness of the water and graphene layers, while the magnitude of the increase in friction was reduced by D2O intercalation. With the help of first-principles density functional theory calculations, we explain this unexpected behavior by the increased spectral range of the vibration modes of graphene caused by water, and by better overlap of the graphene vibration modes with mica phonons, which favors more efficient energy dissipation. The larger increase in friction with H2O versus D2O shows that the high-frequency vibration modes of the water molecules play a very important role in the transfer of the vibrational energy of the graphene to the phonon bath of the substrate.

Pt-based alumina catalysts doped with varying niobium contents (i.e., 0, 1.20, 2.84, and 4.73 wt%, denoted as Pt/Nb–Al2O3) were synthesized via stepwise impregnation for catalytic CO oxidation. The effective incorporation of Nb species without altering the fundamental properties of the Al2O3 support was confirmed by the characterization using XRD, Raman, and TEM. Pt metallic particles were uniformly deposited on the niobium-doped alumina (Nb–Al2O3) support. H2-TPR and CO–TPD analyses were performed to reveal the influence of niobium doping on catalyst reduction and CO adsorption properties. The results consistently demonstrate that the doping of niobium affects reducibility and alleviates the competitive adsorption between CO and O2 during the CO reaction. Particularly, when compared to both undoped and excessively doped Pt/Al2O3 catalysts, the catalyst featuring a 2.84 wt% Nb content on Pt1.4/Nb2.8–Al2O3 displayed the most promising catalytic performance, with a turnover frequency of 3.12 s−1 at 180 °C. This superior performance can be attributed to electron transfer at the Pt/NbOx interface. [ABSTRACT FROM AUTHOR]

Thermal energy transport across the interfaces of physically and chemically modified graphene with two metals, Al and Cu, was investigated by measuring thermal conductance using the time-domain thermoreflectance method. Graphene was processed using a He2+ ion-beam with a Gaussian distribution or by exposure to ultraviolet/O3, which generates structural or chemical disorder, respectively. Hereby, we could monitor changes in the thermal conductance in response to varying degrees of disorder. We find that the measured conductance increases as the density of the physical disorder increases, but undergoes an abrupt modulation with increasing degrees of chemical modification, which decreases at first and then increases considerably. Moreover, we find that the conductance varies inverse proportionally to the average distance between the structural defects in the graphene, implying a strong in-plane influence of phonon kinetics on interfacial heat flow. We attribute the bimodal results to an interplay between the distinct effects on graphene's vibrational modes exerted by graphene modification and by the scattering of modes.

Carrier multiplication (i.e. generation of multiple electron-hole pairs from a single high-energy electron, CM) in graphene has been extensively studied both theoretically and experimentally, but direct application of hot carrier multiplication in graphene has not been reported. Here, taking advantage of efficient CM in graphene, we fabricated graphene/TiO2 Schottky nanodiodes and found CM-driven enhancement of quantum efficiency. The unusual photocurrent behavior was observed and directly compared with Fowler's law for photoemission on metals. The Fowler's law exponent for the graphene-based nanodiode is almost twice that of a thin gold film based diode; the graphene-based nanodiode also has a weak dependence on light intensity-both are significant evidence for CM in graphene. Furthermore, doping in graphene significantly modifies the quantum efficiency by changing the Schottky barrier. The CM phenomenon observed on the graphene/TiO2 nanodiodes can lead to intriguing applications of viable graphene-based light harvesting.

Plasmonic photoelectrochemical (PEC) water splitting has excited immense interest, as it can overcome the intrinsic limitations of semiconductors, in terms of light absorption, by the localized-surface plasmon resonances effect. Here, to get insight into the role of plasmonic hot carriers in plasmonic water splitting, a rational design of an antenna–reactor type Pt/Ag/TiO2 metal–semiconductor Schottky nanodiode was fabricated and used as a photoanode. Using the designed PEC cell system combined with the Pt/Ag/TiO2 nanodiode, we show that the plasmonic hot carriers excited from Ag were utilized for the oxygen (O2) evolution reaction and, consequently, had a decisive role in the enhancement of the photocatalytic efficiency. These results were supported by finite-difference time-domain simulations, and the faradaic efficiency was measured by the amount of actual gas produced. Therefore, this study provides a deep understanding of the dynamics and mechanisms of plasmonic hot carriers in plasmonic-assisted PEC water splitting. [ABSTRACT FROM AUTHOR]

In the last decade, contact electrification has gained attention for its potential in energy harvesting, addressing fundamental physics. Scanning probe microscopy (SPM) has evolved as a powerful platform, enabling the in situ characterization/manipulation of a sample's tribological/electrical properties at nanoscale. However, although both the sliding and tapping modes are available in the energy harvesting, the lateral sliding using contact mode SPM has predominantly been employed in triboelectric study. In this work, contact electrification on polydimethylsiloxane is investigated, using peak force tapping atomic force microscopy (PF‐AFM). As PF‐AFM quasi‐discretely offers vertical tapping motions of the probe with a regulated force amplitude, resembling a vertical‐type triboelectric nanogenerator, while minimizing lateral forces. The subsequent surface potential measurements reveal that the generated tribocharge is influenced by both the effective work function difference and energy dissipation at the interface. Furthermore, the accumulation of transferred charges is explored by measuring tip‐sample current during the PF‐AFM operation, showing the comparable results with the surface potential measurement. The results can be attributed to the contact potential difference assisted by the energy dissipation at the interface. This study offers an advanced opportunity to understand and study charge generation behavior based on surface properties without damaging the sample. [ABSTRACT FROM AUTHOR]

The structure of water confined in nanometer-sized cavities is important because, at this scale, a large fraction of hydrogen bonds can be perturbed by interaction with the confining walls. Unusual fluidity properties can thus be expected in the narrow pores, leading to new phenomena like the enhanced fluidity reported in carbon nanotubes. Crystalline mica and amorphous silicon dioxide are hydrophilic substrates that strongly adsorb water. Graphene, on the other hand, interacts weakly with water. This presents the question as to what determines the structure and diffusivity of water when intercalated between hydrophilic substrates and hydrophobic graphene. Using atomic force microscopy, we have found that while the hydrophilic substrates determine the structure of water near its surface, graphene guides its diffusion, favouring growth of intercalated water domains along the C-C bond zigzag direction. Molecular dynamics and density functional calculations are provided to help understand the highly anisotropic water stripe patterns observed.