Project description:The polaron introduced by the oxygen vacancy (Vo) dominates many surface adsorption processes and chemical reactions on reduced oxide surfaces. Based on IR spectra and DFT calculations of NO and CO adsorption, we gave two scenarios of polaron-involved molecular adsorption on reduced TiO2(110) surfaces. For NO adsorption, the subsurface polaron electron transfers to a Ti:3d-NO:2p hybrid orbital mainly on NO, leading to the large redshifts of vibration frequencies of NO. For CO adsorption, the polaron only transfers to a Ti:3d state of the surface Ti5c cation underneath CO, and thus only a weak shift of vibration frequency of CO was observed. These scenarios are determined by the energy-level matching between the polaron state and the LUMO of adsorbed molecules, which plays a crucial role in polaron-adsorbate interaction and related catalytic reactions on reduced oxide surfaces.
Project description:The massively parallel arrays of highly periodic Gd-doped Si nanowires (SiNWs) self-organized on Si(110)-16 × 2 surface were investigated by scanning tunneling microscopy and spectroscopy. These periodic Gd-doped SiNWs are atomically precise and show equal size, periodic positions, and high-integration densities. Surprisingly, the scanning tunneling spectroscopy results show that each metallic-like, Gd-doped SiNW exhibits room-temperature negative differential resistance (RT-NDR) behavior, which can be reproducible with various Gd dopings and is independent of the tips. Such massively parallel arrays of highly ordered and atomically identical Gd-doped SiNWs with one-dimensional laterally confined RT-NDR can be exploited in Si-based RT-NDR nanodevices.
Project description:The in situ metalation of tetraphenylporphyrin (2HTPP) with Ni on the reconstructed TiO2(110)-1 × 2 surface, resulting in the formation of adsorbed nickel(II)-tetraphenylporphyrin (NiTPP), has been investigated by synchrotron radiation photoemission spectroscopy (SRPES), scanning tunnelling microscopy (STM) and ab initio Density Functional Theory (DFT) calculations. The metalation can be realized at room temperature irrespective of the deposition order of Ni and 2HTPP, which however leads to different metalation degrees. Increasing the substrate temperature or Ni : 2HTPP ratio results in higher metalation degree, which ultimately reaches its limit at ∼85% (Ni : 2HTPP = 3 : 1) and ∼49% (Ni : 2HTPP = 1 : 1) for post- and pre-deposition of Ni, respectively. The reaction from 2HTPP to NiTPP is accompanied by changes of the molecular adsorption conformation and the adsorption site from a tilted two-lobed feature on added Ti2O3 rows to a four-lobed feature on top of troughs or cross-links of the TiO2(110)-1 × 2 surface. This interpretation of the STM data is supported by DFT-based STM simulations.
Project description:Ceramic materials have been widely used for structural applications. However, most ceramics have rather limited plasticity at low temperatures and fracture well before the onset of plastic yielding. The brittle nature of ceramics arises from the lack of dislocation activity and the need for high stress to nucleate dislocations. Here, we have investigated the deformability of TiO2 prepared by a flash-sintering technique. Our in situ studies show that the flash-sintered TiO2 can be compressed to ~10% strain under room temperature without noticeable crack formation. The room temperature plasticity in flash-sintered TiO2 is attributed to the formation of nanoscale stacking faults and nanotwins, which may be assisted by the high-density preexisting defects and oxygen vacancies introduced by the flash-sintering process. Distinct deformation behaviors have been observed in flash-sintered TiO2 deformed at different testing temperatures, ranging from room temperature to 600°C. Potential mechanisms that may render ductile ceramic materials are discussed.
Project description:In this manuscript a near-room temperature crystallization process of anodic nanotubes from amorphous TiO2 to anatase phase with a fast 30 minutes treatment is reported for the first time. This method involves the exposure of as-grown TiO2 nanotubes to water vapor flow in ambient atmosphere. The water vapor-crystallized samples are deeply investigated in order to gain a whole understanding of their structural, physical and chemical properties. The photocatalytic activity of the converted material is tested by dye degradation experiment and the obtained performance confirms the highly promising properties of this low-temperature processed material.
Project description:A high-performance gas sensor operating at room temperature is always favourable since it simplifies the device fabrication and lowers the operating power by eliminating a heater. Herein, we fabricated the ammonia (NH3) gas sensor by using Au nanoparticle-decorated TiO2 nanosheets, which were synthesized via two distinct processes: (1) preparation of monolayer TiO2 nanosheets through flux growth and a subsequent chemical exfoliation and (2) decoration of Au nanoparticles on the TiO2 nanosheets via hydrothermal method. Based on the morphological, compositional, crystallographic, and surface characteristics of this low-dimensional nano-heterostructured material, its temperature- and concentration-dependent NH3 gas-sensing properties were investigated. A high response of ~ 2.8 was obtained at room temperature under 20 ppm NH3 gas concentration by decorating Au nanoparticles onto the surface of TiO2 nanosheets, which generated oxygen defects and induced spillover effect as well. Supplementary Information The online version contains supplementary material available at 10.1186/s11671-023-03798-5.
Project description:The discovery of hydrogen atoms on the TiO2 surface is crucial for many practical applications, including photocatalytic water splitting. Electronically activating interfacial hydrogen atoms on the TiO2 surface is a common way to control their reactivity. Modulating the potential landscape is another way, but dedicated studies for such an activation are limited. Here we show the single hydrogen atom manipulation, and on-surface facilitated water deprotonation process on a rutile TiO2 (110) surface using low temperature atomic force microscopy and Kelvin probe force spectroscopy. The configuration of the hydrogen atom is manipulated on this surface step by step using the local field. Furthermore, we quantify the force needed to relocate the hydrogen atom on this surface using force spectroscopy and density functional theory. Reliable control of hydrogen atoms provides a new mechanistic insight of the water molecules on a metal oxide surface. Rutile TiO2 is a prominent photocatalyst for overall water splitting, but the on-surface activation of hydrogen atoms is still not fully understood. Here, the authors use atomic force and kelvin probe force microscopy to study the lateral manipulation of hydrogen on a rutile (110) surface.
Project description:Oxygen vacancies on metal oxide surfaces have long been thought to play a key role in the surface chemistry. Such processes have been directly visualized in the case of the model photocatalyst surface TiO(2)(110) in reactions with water and molecular oxygen. These vacancies have been assumed to be neutral in calculations of the surface properties. However, by comparing experimental and simulated scanning tunneling microscopy images and spectra, we show that oxygen vacancies act as trapping centers and are negatively charged. We demonstrate that charging the defect significantly affects the reactivity by following the reaction of molecular oxygen with surface hydroxyl formed by water dissociation at the vacancies. Calculations with electronically charged hydroxyl favor a condensation reaction forming water and surface oxygen adatoms, in line with experimental observations. This contrasts with simulations using neutral hydroxyl where hydrogen peroxide is found to be the most stable product.
Project description:The field of isomerization reactions for colloidal semiconductor magic-size clusters (MSCs) remains largely unexplored. Here, we show that MSCs isomerize via two fundamental pathways that are regulated by the acidity and amount of an incoming ligand, with CdTeSe as the model system. When MSC-399 isomerizes to MSC-422 at room temperature, the peak red-shift from 399 to 422 nm is continuous (pathway 1) and/or stepwise (pathway 2) as monitored in situ and in real time by optical absorption spectroscopy. We propose that pathway 1 is direct, with intracluster configuration changes and a relatively large energy barrier. Pathway 2 is indirect, assisted by the MSC precursor compounds (PCs), from MSC-399 to PC-399 to PC-422 to MSC-422. Pathway 1 is activated when PC-422 to MSC-422 is suppressed. Our findings unambiguously suggest that when a change occurs directly on a nanospecies, its absorption peak continuously shifts. The present study provides an in-depth understanding of the transformative behavior of MSCs via ligand-induced isomerization upon external chemical stimuli.