We prepared ZnO ultrafine particles (UFPs) by thermal decomposition of the precursor zinc carbonate hydroxide. The surface properties of the as-prepared particles were studied using TEM, XRD, BET, SPS, EPR, IR, and XPS. The surface contains active species such as oxygen deficiencies and hydroxyl that improve photocatalytic activities. The concentrations of active species decreased as the calcination temperature increased along with the surface areas and photovoltage. The ZnO UFP have a significant EPR signal resulting from O2 deficiencies on the surface, which can capture and trap alectrons. Dining photocatalytic degradation of phenol, the photocatalytic activities of the particles decreased as their size increased, which means that these activities depend mainly on surface properties.

In this paper, ZnO ultrafine particles (UFPs) were prepared by the thermal decomposition method of the precursor, zinc carbonate hydroxide. The structure and properties of the as-prepared ZnO UFPs were studied using TEM, XRD, BET, SPS, ESR, Raman, XPS and UV-Vis absorption spectroscopy. It was found that the prepared ZnO UFPs exhibited obvious quantum size effect and surface effect. In addition, there were many active species on the surface of ZnO UFPs such as oxygen deficiencies and hydroxyls, both of which can improve the photocatalytic activities of ZnO UFPs.

Nanoparticle TiO2/Ti films were prepared by a sol-gel process using Ti(OBu)4 as raw material, the as-prepared film samples were also characterized by TG-DTA, XRD, TEM, SEM, XPS, DRS, PL, SPS and EFISPS testing techniques. TiO2 nanoparticles experienced two processes of phase transition, i.e. amorphous to anatase and anatase to rutile at the calcining temperature range from 450 to 700℃. TiO2 nanoparticles calcined at 600℃ had similar composition, structure, morphology and particle size with the internationally commercial P-25 TiO2 particles. Thus, the conclusion that 600℃ might be the most appropriate calcining temperature during the preparation process of nanoparticle TiO2/Ti film photocatalysts could be made by considering the main factors such as the properties of TiO2 nanoparticles, the adhesion of nanoparticle TiO2 film to Ti substrate, the effects of calcining temperature on Ti substrate and the surface characteristics and morphology of nanoparticle TiO2/Ti film for the practice view. The Ti element mainly existed on the nanoparticle TiO2/Ti(3) film calcined at 600℃ as the chemical state of Ti4þ, while O element mainly existed as three kinds of chemical states, i.e. crystal lattice oxygen, hydroxyl oxygen and adsorbed oxygen with increasing band energy. Its photoluminescence (PL) spectra with a peak at about 380 nm could be observed using 260nm excitation, possibly resulting from the electron transition from the bottom of conduction band to the top of valence band. The PL peak position was nearly the same as the onset of its diffuse reflection spectra (DRS) and surface photovoltage spectroscopy (SPS), demonstrating that the effects of the quantum size on optical property were greater than that of the Coulomb and surface polarization. The PL spectra with two peaks related to the anatase and rutile, respectively, could be observed using the excited wavelength of 310 nm. Weak PL spectra could be observed using the excited wavelength of 450 nm, resulting from surface states. In addition, during the experimental process of the photocatalytic degradation phenol, the photocatalytic activity of nanoparticle TiO2/Ti film with three layers calcined at 600℃ was the highest.

In this paper, pure and La doped TiO2 nanoparticles with different La content were prepared by a sol-gel process using Ti (OC4H9)4 as raw material, and also were characterized by XRD, TG-DTA, TEM, XPS, DRS and Photoluminescence (PL) spectra. We mainly investigated the effects of calcining temperature and La content on the properties and the photocatalytic activity for degrading phenol of as-prepared TiO2 samples, and also discussed the relationships between PL spectra and photocatalytic activity as well as the mechanisms of La doping on TiO2 phase transformation. The results showed that La3+ did not enter into the crystal lattices of TiO2 and was uniformly dispersed onto TiO2 as the form of La2O3 particles with small size, which possibly made La dopant have a great inhibition on TiO2 phase transformation; La dopant did not give rise to a new PL signal, but it could improve the intensity of PL spectra with a appropriate La content, which was possibly attributed to the increase in the content of surface oxygen vacancies and defects after doping La; La doped TiO2 nanoparticles calcined at 600℃ exhibited higher photocatalytic activity, indicating that 600℃ was an appropriate calcination temperature. The order of photocatalytic activity of La doped TiO2 samples with different La content was as following: 141.54340.54540 mol%, which was the same as the order of their PL intensity, namely, the stronger the PL intensity, the higher the photocatalytic activity, demonstrating that there were certain relationships between PL spectra and photocatalytic activity. This could be explained by the points that PL spectra mainly resulted from surface oxygen vacancies and defects during the process of PL, while surface oxygen vacancies and defects could be favorable in capturing the photoinduced electrons during the process of photocatalytic reactions.

Heterogeneous photocatalysis is a promising technique valuable for environmental purification. Nano-sized semiconductors such as ZnO and TiO2, which is one of the most basic functional materials, have emerged as effective photocatalyst materials. The surface photovoltage spectra (SPS) can be an effective method for quickly evaluating the photocatalytic activity of semiconductor materials since it can provide a rapid, non-destructive monitor of the semiconductor surface properties such as surface band bending, surface and bulk carrier recombination and surface states, mainly showing the carrier separation and transfer behavior with the aid of light, especially the electric-field-induced surface photovoltage spectra (EFISPS), in which SPS is combined with the electric-field-modified technique. In this review, the basic principles, measurement and applications of the SPS and EFISPS are mainly discussed together with some fundamental aspects like the electric properties of semiconductor surface and the principle of electric field effect. In particular, the applications of SPS to nano-sized semiconductors such as ZnO and TiO2 in heterogeneous photocatalysis are emphasized, which involve mainly evaluating the photocatalytic activity by analyzing semiconductor surface properties such as the separation efficiency of photoinduced carriers under illumination by the SPS measurement, highlighting our own contributions. The results show that the weaker the surface photovoltage signal is, the higher the photocatalytic activity is in the case of nano-sized semiconductor photocatalysts.