Interferometric two-photon photoemission correlation technique and femtosecond wet-electron dynamics at the TiO2(110) surface

The femtosecond time-resolved two-photon photoemission (TR-2PP) and the ultra high vacuum (UHV) surface science techniques are integrated to investigate the electronic structures and the interfacial electron transfer dynamics at the atomically ordered adsorbate overlayers on TiO₂ singlecrystalline surfaces. Our research into the CH₃OH/TiO₂ system exhibits complex dynamics, providing abundant information with regard to electron transport and solvation processes in the interfacial solvent structures. These represent the fundamentally physical, photochemical, and photocatalytic reactions of protic chemicals covered with metal-oxides.     

Surface-initiated atom transfer radical polymerization from TiO2 nanoparticles

Two kinds of hydrophilic polymers, poly(oxyethylene methacrylate) (POEM) and poly(styrene sulfonic acid) (PSSA), were grafted from TiO₂ nanoparticles via the surface-initiated atom transfer radical polymerization (ATRP) technique. Chlorine modified TiO₂ nanoparticles (TiO₂-Cl), the ATRP initiators, were synthesized by the reaction of -OH in TiO₂ with 2-chloropropionyl chloride (CPC). FT-IR, UV-vis spectroscopy and X-ray photoelectron spectroscopy (XPS) clearly showed that the polymer chains were successfully grafted from the surface of TiO₂ nanoparticles. The hydrophilically modified TiO₂ nanoparticles have a better dispersion in alcohol than unmodified nanoparticles, as revealed by transmission electron microscopy (TEM). It was also found that the polymer grafting did not significantly alter the crystalline structure of the TiO₂ nanoparticles according to the X-ray diffraction (XRD) patterns. Grafting amounts were 10% of the weight for both TiO₂-POEM and TiO₂-PSSA nanoparticles, as determined by thermogravimetric analysis (TGA).     

Controlled synthesis of TiO2-B nanowires and nanoparticles for dye-sensitized solar cells

Controllable synthesis of the TiO₂-B nanowires (NWs) and nanoparticles (NPs) had been achieved via a facile hydrothermal route, respectively, only by tuning the solution volume. The dye-sensitized solar cells prototypes had been fabricated using TiO₂-B NW and NP electrodes, respectively. The TiO₂-B NP cells had higher photocurrent and photoelectrical conversion efficiency than the TiO₂-B NW cells though the latter exhibited larger photovoltage compared to the former. The key factors such as the photogenerated electron injection drive force, surface defects and the interfacial charge transfer, which determined the photoelectrical properties, had been systematically researched with the surface photovoltage spectra (SPS) and the electrochemical impedance spectra (EIS). The SPS proved that there was larger photoelectron injection drive force in TiO₂-B NP photoelectrode than that in NW photoelectrode. And the electrochemical impedance spectra (EIS) revealed that TiO₂-B NP cells had faster interface charge transfer compared to TiO₂-B NW cells. Both proved that NP cells had the higher photocurrents.     

A surface science perspective on TiO2 photocatalysis

The field of surface science provides a unique approach to understanding bulk, surface and interfacial phenomena occurring during TiO₂ photocatalysis. This review highlights, from a surface science perspective, recent literature that provides molecular-level insights into photon-initiated events occurring at TiO₂ surfaces. Seven key scientific issues are identified in the organization of this review. These are: (1) photon absorption, (2) charge transport and trapping, (3) electron transfer dynamics, (4) the adsorbed state, (5) mechanisms, (6) poisons and promoters, and (7) phase and form. This review ends with a brief examination of several chemical processes (such as water splitting) in which TiO₂ photocatalysis has made significant contributions in the literature.     

Dye-sensitized solar cells based on ZnO nanowire array/TiO2 nanoparticle composite photoelectrodes with controllable nanowire aspect ratio

The ZnO nanowire (NW) array/TiO₂ nanoparticle (NP) composite photoelectrode with controllable NW aspect ratio has been grown from aqueous solutions for the fabrication of dye-sensitized solar cells (DSSCs), which combines the advantages of the rapid electron transport in ZnO NW array and the high surface area of TiO₂ NPs. The results indicate that the composite photoelectrode achieves higher overall photoelectrical conversion efficiency (η) than the ZnO NW alone. As a result, DSSCs based on the ZnO NW array/TiO₂ NP composite photoelectrodes get the enhanced photoelectrical conversion efficiency, and the highest η is also achieved by rational tuning the aspect ratio of ZnO NWs. With the proper aspect ratio (ca. 6) of ZnO NW, the ZnO NW array/TiO₂ NP composite DSSC exhibits the highest conversion efficiency (5.5 %). It is elucidated by the dye adsorption amount and interfacial electron transport of DSSCs with the ZnO NW array/TiO₂ NP composite photoelectrode, which is quantitatively characterized using the UV-Vis absorption spectra and electrochemical impedance spectra. It is evident that the DSSC with the proper aspect ratio of ZnO NW displays the high dye adsorption amount and fastest interfacial electron transfer.     

Interfacial electronic structure and ion beam induced effect of anatase TiO2 surface modified by Pd nanoparticles

Anatase TiO₂ surface could be modified by Pd nanoparticles using an electrochemical deposition method. Surface morphology, light absorption and interfacial electronic structures were studied by field emission scanning electron microscopy (FE-SEM), UV-visible reflectance absorption, X-ray diffraction (XRD) crystallography, and depth-profiling X-ray photoelectron spectroscopy (XPS). On the basis of XRD patterns, Pd 3d XPS and valance band spectra, the as-deposited overlayer Pd is metallic, with no detectable Pd oxides. The optical band gap of TiO₂ decreases from 3.25 to 3.14 eV upon Pd deposition. The XPS spectra with Ar⁺ ion sputtering show that 4+ oxidation state of Ti dramatically changes to lower (3+ and 2+) oxidation states. As a result of this, oxygen defects are created in the bulk while the oxygen diffuses outward to likely form hydroxyl group on the surface. The Pd 3d XPS peak shifts by +0.6 eV to a higher BE position, and the density of state at the Fermi level is more or less reduced. It appears that the overlayer Pd becomes less metallic, plausibly due to TiO₂ support and/or size effect. No critical interfacial interaction between Pd and TiO₂ was observed by XPS.     

乙醇在TiO2(110)表面光催化解离的动力学和超快电子动态学 (cited: 2)

采用实时双光子光电子能谱和时间分辨双光子光电子能谱技术分别研究了乙醇在该表面光催化解离的动力学和超快电子动态学过程. 通过测量与乙醇光催化解离相关的电子激发态随时间的演化,发现这个反应满足分型动力学. 乙醇在还原性TiO₂(110)上的光催化解离比在氧化性表面快,这归结于缺陷的存在降低了反应能垒. 这样一个反应的加速过程很可能是与缺陷电子相关的. 通过干涉双脉冲相关的测量,得到了乙醇-TiO₂界面电子激发态的超快动态学. 与甲醇的情况类似,这个电子激发态的寿命为24 fs. 激发态的出现为TiO₂和它周围环境的电子转移提供了一个通道.     

Epitaxial growth defects and interfacial structures of Cu deposited on TiO2

Epitaxial growth defects and the interfacial structure between vapor deposited Cu and TiO₂(110) have been studied by combined high-resolution electron microscopy (HREM) and image simulations. The Cu film was found to grow epitaxially with an orientation given by Cu(111)//TiO₂(110) and Cu110//TiO₂ [001]. With this relationship, there exist two equivalent domain orientations which are rotated with respect to each other by 180°. Localized misfit dislocations have not been detected, but {111} stacking faults and microtwins were observed which may occur as a result of 3-D island coalescence. HREM observations and image simulations have been used to study the interface atomic structure. The dominant interfacial structure has a stoichiometric (110) TiO₂ surface with bridging rows of O atoms and occasionally, an interfacial structure having a reduced (110) TiO₂ surface terminated by both Ti and O atoms has been observed locally.     

Synthesis and characterization of TiO2/Ag/polymer ternary nanoparticles via surface-initiated atom transfer radical polymerization

We report on the novel ternary hybrid materials consisting of semiconductor (TiO₂), metal (Ag) and polymer (poly(oxyethylene methacrylate) (POEM)). First, a hydrophilic polymer, i.e. POEM, was grafted from TiO₂ nanoparticles via the surface-initiated atom transfer radical polymerization (ATRP) technique. These TiO₂-POEM brush nanoparticles were used to template the formation of Ag nanoparticles by introduction of a AgCF₃SO₃ precursor and a NaBH₄ aqueous solution for reduction process. Successful grafting of polymeric chains from the surface of TiO₂ nanoparticles and the in situ formation of Ag nanoparticles within the polymeric chains were confirmed using transmission electron microscopy (TEM), UV-vis spectroscopy, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). FT-IR spectroscopy also revealed the specific interaction of Ag nanoparticles with the CO groups of POEM brushes. This study presents a simple route for the in situ synthesis of both metal and polymer confined within the semiconductor, producing ternary hybrid inorganic-organic nanomaterials.     

Investigation of Interfacial Charge Separation at PbS QDs/(001) TiO2 Nanosheets Heterojunction Solar Cell

In the recent years, the heterojunction solar cells based on quantum dots (QDs) have attracted attention due to strong light absorbing characteristics and the size effect on the bandgap tuning. This paper reports on the kinetics of interfacial charge separation of PbS QDs/(001) TiO₂ nanosheets heterojunction solar cells. PbS QDs are deposited using a bifunctional linker molecule on two different TiO₂ films, i.e., TiO₂ nanosheets (with 001 dominant exposed facet) and TiO₂ nanoparticles (with 101 dominant exposed facet). Upon bandgap excitation, electrons are transferred from the PbS QDs conduction band to the lower lying conduction band of TiO₂. Based on the ultrafast pump‐probe laser spectroscopy technique, the kinetics of charge separation is scrutinized at the PbS/TiO₂ interface. The interfacial charge separation at PbS/TiO₂ nanosheets films made of (001) dominant exposed facets is five times faster than that on (101) dominant exposed facets TiO₂ nanoparticles. The quantum yields for charge injection are higher for the (001) TiO₂ nanosheets than the (101) TiO₂ nanoparticles due to enhanced interfacial interaction with (001) surface compared to the (101) nanoparticles. The superior interfacial charge separation at PbS/(001) nanosheets respect to PbS/(101) nanoparticles is consistent with the higher photocurrent and enhanced power conversion efficiency in the PbS QDs/(001) TiO₂ heterojunction solar cell. The use of (001) TiO₂ nanosheets can be a better alternative to conventional mesoporous TiO₂ films in QD heterojunction solar cells and perovskites‐based heterojunction solar cells.