In this paper, ZnO nanoparticle photocatalysts were modified by depositing Pd on their surfaces with a photoreduction method. We mainly investigated the modification mechanisms as well as the effects on the photocatalytic activity of ZnO nanoparticles of deposited Pd by means of XPS and SPS (Surface Photovoltage Spectroscopy), and the effects of Pd content on SPS responses were also discussed from the point of the electronic energy level. The results showed that the content of crystal lattice oxygen on the surface of ZnO nanoparticle decreased after an appropriate amount of Pd was deposited, while that of adsorbed oxygen increased, indicating that Pd was mainly deposited on the crystal lattice oxygen. At the same time, the intensity of SPS responses of ZnO nanoparticles remarkably decreased. In addition, the activity of ZnO nanoparticles could be greatly improved by depositing an appropriate amount of Pd in the gas phase photocatalytic oxidation of n-C7H16. Thus, it could be concluded that the increase in surface content of adsorbed oxygen could facilitate the photocatalytic reaction, and there were close relationships between the SPS response and photocatalytic activity, i.e. the weaker the SPS response, the higher the photocatalytic activity, of Pd-deposited ZnO nanoparticles.

In this paper, we examined the lifetimes of made-in-home ZnO and TiO2 nanoparticles in the gas phase photocatalytic oxidation of n-C7H16 or SO2, and especially investigated the deactivation mechanism by utilizing surface photovoltage spectrum (SPS) and X-Ray photoelectron spectroscopy (XPS) testing techniques and by considering semiconductor chemical properties. The results showed that ZnO could almost be deactivated in the gas phase photocatalytic oxidation of n-C7H16, while TiO2 could keep most of its activity. In the gas phase photocatalytic oxidation of n-C7H16 or SO2, ZnO and TiO2 both could almost be deactivated. The deactivation mainly resulted from semiconductor surface conduction type change from N-type before the photocatalytic reaction to P-type after the deactivation because of the adsorption of the oxidation products such as H2O, CO2 and SO3 on the semiconductor photocatalyst surface. In addition, the activity of the deactivated photocatalyst could be regenerated to a nearly full extent by washing and drying.

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.

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.

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.