Nanostructured PbSnO3photocatalysts with particulate and tubular morphologies have been synthesized from a simple hydrothermal process. As-prepared samples were characterized by X-ray diffraction, Brunauer–Emmet–Teller surface area, transmission electron microscopy, and diffraction spectroscopy. The photoactivities of the PbSnO3nanostructures for isopropanol (IPA) degradation under visible light irradiation were investigated systematically, and the results revealed that these nanostructures show much higher photocatalytic properties than bulk PbSnO3material. The possible growth mechanism of tubular PbSnO3catalyst was also investigated briefly.
Since the Honda–Fujishima effect was reported in 1972, considerable efforts have been paid to develop semiconductor photocatalysts for water splitting and degradation of organic pollutants in order to solve the urgent energy and environmental issues [1-9]. However, to date, most of the photocatalysts reported only respond to UV light irradiation (<420 nm). For visible light accounts for about 43% of the solar spectrum, the utilization of visible light is more significant than UV light and thus developing visible light-driven photocatalyst is one of the most important and meaningful subjects in this field. The fundamental steps for photocatalytic reaction of oxide semiconductor mainly include the following processes: (i) the generation of photoexited charges in the semiconductor materials, (ii) the separation and migration of the generated charges without recombination, and (iii) the redox reaction on the surface of the semiconductor. The first and second steps are associated with the electronic structures of the oxide semiconductor, while the third step is strongly relevant to the surface properties of the catalyst [10-12].
Generally, the improvement of surface area always contributes to more reaction sites, which is beneficial to the photocatalytic reaction. With particular microstructures, nanomaterials have recently gained much attention to be used as high-performance photocatalysts with enhanced photocatalytic activities. For example, in our previous work, we reported the synthesis of perovskite SrSnO3 nanostructures  from a facile hydrothermal method. Compared with the catalyst from the traditional solid state route, nanostructured SrSnO3 catalysts with larger surface areas showed higher photocatalytic activities for water splitting under UV light irradiation. Undoubtedly, the enhanced photocatalytic activities are mainly attributed to the increased surface areas, which are believed to be one of the efficient approaches to enhance the activity of catalysts. From a similar hydrothermal process, we reported here the preparation of a new visible light-responded photocatalyst, PbSnO3 nanostructures including particulate and tubular shapes. Experimental results confirmed that these nanostructures show distinguished photocatalytic oxidation activity upon mineralizing isopropanol (IPA) into CO2 in the visible light region.
Synthesis of PbSnO3Nanostructures
For the synthesis of tubular PbSnO3nanostructures, two same surfactant–water solutions were first prepared by dissolving 0.2 g poly(vinyl pyrrolidone) (PVP) surfactant in 25 mL distilled water, respectively. Then, equivalent amounts of Pb(AC)2and Na2SnO3(2 mmol) were dissolved in the above surfactant–water solution at room temperature, separately. After stirred for 30 min, the solutions were mixed together and kept stirring for another 30 min, which were then transferred into a Teflon-lined stainless steel autoclave and subsequently heated at 180 °C for 16 h in an oven. After cooling to room temperature, the yellow precipitate was filtered and washed for several times with distilled water and ethanol, respectively, then dried in air at 70 °C. PbSnO3nanoparticles were also synthesized in this work using a similar process without the use of surfactant PVP. Brief flowcharts illustrating the formation of PbSnO3nanostructures are shown in Scheme 1.
Synthesis of Bulk PbSnO3from SSR
To compare the photocatalytic properties, bulk PbSnO3was also synthesized by selecting optimal experimental parameters including calcinations temperature and time. For the synthesis of PbSnO3bulk material, we first dissolved equivalent amounts of Pb(AC)2and Na2SnO3into distilled water under stirring, and then mixed them to obtain the white precursor. Heating the white precursor at 500 °C for 5 h in a quartz tube under Ar flow resulted in yellow powders. In this process, temperature is very important for the formation of yellow powders due to the instability of PbSnO3at high temperature.
The crystal structure of the as-prepared sample was confirmed by the X-ray diffraction pattern (JEOL JDX-3500 Tokyo, Japan). The morphology and size of the sample were characterized by transmission electron microscope (HRTEM, JEM-3000F) equipped with an X-ray dispersive spectrometer (EDS). UV–Vis diffuse reflectance spectra were recorded on a UV/Vis spectrometer (UV-2500, Shimadzu) and were converted from reflection to absorbance by the standard Kubelka–Munk method. The surface area of the sample was measured by the BET method (Shimadsu Gemini Micromeritics).
Evolution of Photocatalytic Property
The photoactivities of the obtained PbSnO3nanostructures were evaluated by decomposition of gaseous IPA under visible light irradiation. Typically, 0.1 g PbSnO3catalyst was spread uniformly in a quartz-made vessel with an irradiation area of 7.8 cm2. Prior to light irradiation, the vessel was kept in dark for 2 h until an adsorption–desorption equilibrium was finally established. The visible light with light intensity of about 1.8 mW/cm2was obtained by using a 300 W Xe lamp with a set of combined filters (L42 + B390 + HA30) and a water filter. The products in the gas phase were analyzed with a gas chromatograph system (GC-14B, Shimadzu, Japan), using a flame ionization detector (FID) for organic compounds determination.
Results and Discussion
Crystal Structure and Morphology
The crystal structure of both as-synthesized PbSnO3nanostructures from the hydrothermal process and bulk material from the solid-state route were characterized by XRD and the results are shown in Fig. 1. In these patterns, all peaks can be indexed as cubic phase PbSnO3with pyrochlore-type structure (space group:Fd3m). The calculated lattice constanta = 10.67 Å is in agreement with previously reported value (JCPDS 17-060). From the XRD patterns, it can be clearly seen that the PbSnO3nanostructures are of better crystallinity than the bulk material, which might be one of the reasons why nanostructured PbSnO3show higher photocatalytic activities (detailed contents in the part of discussion). Inset in Fig. 1is a typical SEM image of the product from the SSR. Scheme 2 shows the crystal structure of pyrochlore-type PbSnO3, an anion-deficient three-dimensional framework consisting of corner-sharing SnO6octahedra.
Figure 1. XRD patterns of the as-prepared PbSnO3nanostructures from the hydrothermal route and bulk samples from the solid-state route, respectively. Inset shows SEM image of bulk material from SSR
Figure 2a shows a TEM image of as-prepared PbSnO3nanoparticles from the hydrothermal process. Obviously, the products are consisted of many small nanoparticles with dimensions in the range of 10–15 nm. The corresponding selected-area electron diffraction (SAED) pattern (Fig. 2b) can be readily indexed as cubic phase PbSnO3, which is in agreement with the XRD result. An EDS spectrum in Fig. 2c depicts the presence of Pb, Sn, and O elements, indicating the formation of PbSnO3. In this spectrum, the signals corresponding to Cu arise from the TEM grid. The microstructures of the produced PbSnO3nanoparticles were investigated using high-resolution TEM. As indicated in Fig. 2d, the nanoparticles are well-crystallized and of good crystallinity. The marked lattice fringes of 0.32 and 0.25 nm correspond well to the (311) and (331) crystalline planes of cubic PbSnO3.
Figure 2. aTEM image;bSAED pattern;cEDS spectrum;dHRTEM image of the as-prepared PbSnO3nanoparticles from the hydrothermal process
In the presence of surfactant PVP, polycrystalline PnSnO3nanotubes were obtained instead of nanoparticles. Panels (a) and (b) of Fig. 3are typical TEM images of as-obtained PnSnO3nanotubes, which reveal that the nanotubes are polycrystalline with typical diameters of 300–340 nm and wall thickness of 40–80 nm. Figure 3c is the corresponding SAED pattern taken from a single PbSnO3nanotube, confirming the formation of polycrystalline nanotube. The three polycrystalline rings are in accordance with those of (311), (400), and (533) of cubic phase PbSnO3. Typical HRTEM images of the nanotubes are shown in Fig. 3d and e. It can be seen that the polycrystalline PbSnO3nanotubes are composed of numerous nanoparticles with diameters of several to ten nanometers. The interplanar spacing was calculated to be about 0.32 nm, corresponding to the (311) plane of cubic PbSnO3, in accordance with the SAED result.
Figure 3. a,bTEM images;cSAED pattern;d,eHRTEM images of the as-prepared PbSnO3nanotubes in the presence of surfactant PVP
UV–Vis spectra of all three PbSnO3samples were checked and the spectra are displayed in Fig. 4. It is evident that PbSnO3nanostructures could absorb much more visible light than bulk sample at the present condition. Corresponding band gaps of PbSnO3are determined to be 2.8 eV for bulk material, 2.8 eV for nanotubes, and 2.7 eV for nanoparticles from the absorption edges, respectively (as shown in Table 1).
Figure 4. UV–Vis diffuse reflectance spectra of PbSnO3nanostructures from the hydrothermal route and PbSnO3particles from the solid-state route, respectively
Table 1. Physical and photocatalytic properties of PbSnO3samples
One-dimensional micro- or nanosized tubular materials with hollow interior structure have attracted extraordinary attention owing to their unique properties and potential applications [14-16]. Many kinds of growth mechanisms have been proposed for the formation of nanotubes. For example, the rolling mechanism and template-assisted mechanism have been reported to explain the formation of tubular structure with layered or pseudo-layered structures such as BN , NiCl2, Nb2O5, Se , etc. During the growth of PbSnO3 nanotubes, surfactant PVP was used and was found to be the key issue for nanotube growth. Thus, the surfactant-assisted growth process can be used to explain the formation of these nanotubes. The possible formation process of PbSnO3 nanotubes may involve three following distinctive stages: (i) the generation of PbSnO3 particles, (ii) the adsorption of PVP molecules on the surface of particles and subsequently self-assembly into tubular microstructure, and (iii) the formation of uniform PbSnO3 nanotubes. In the initial stage, cubic PbSnO3 tiny nuclei could easily crystallize and serve as the seeds for the growth of nanotubes. Meanwhile, PVP molecules in the solution would strongly and rapidly adsorb on the surfaces of these nascent nuclei, which confined the crystal growth and efficiently controlled the dimension and morphology of the final products. Then, these particles with high free energy aggregated and self-assembled into tubular structures with the help of PVP template molecules. As a result, the growth of PbSnO3 nanotubes would form eventually by a typical oriented attachment process under the hydrothermal conditions. Meanwhile, the existence of PVP in this solution can alter the surface energies of various crystallographic surfaces to promote selective anisotropic growth of nanocrystals .
Photocatalytic Degradation of IPA
The photocatalytic activities of the PbSnO3nanostructures were evaluated by IPA mineralization under visible light irradiation. Under visible light irradiation, gaseous IPA was gradually oxidized through an acetone intermediate to CO2, and the concentration changes of IPA, acetone, and CO2versus time over PbSnO3nanoparticles are shown in Fig. 5. It was clear that the concentration of IPA in the reaction system almost decreased from the initial concentration to zero; the concentration of acetone also decreased continually while the concentration of CO2increased with the long-term irradiation. Inset in Fig. 5shows that almost no additional CO2gas was detected under dark test, suggesting that degradation of IPA over the catalyst was driven by light irradiation. Figure 6further displays the concentration changes of evolved acetone over different PbSnO3nanostructures and bulk material with the increasing of irradiation time. Clearly, acetone was detected over all these catalysts when light was turned on. Among them, particulate PnSnO3performs the best activity for degradation of IPA under the present conditions.
Figure 5. Changes of IPA, acetone, and CO2concentrations as a function of time in the presence of PbSnO3nanoparticles from the hydrothermal process under visible light irradiation (catalyst: 0.1 g, 300 W Xe lamp, 420 nm cutoff filter and water filter). Inset shows that no CO2gas was evolved turning off the light
Figure 6. Acetone evolution from IPA photodegradation over serious PbSnO3samples (catalyst: 0.1 g, 300 Xe lamp, L42 + B390 + HA30 and water filter)
In this case, the photocatalytic activities for IPA degradation over these catalysts were in the order of nanoparticle > nanotube > bulk material, which was in consistent with that of BET surface areas. As mentioned earlier, BET surface area of catalyst is closely related to its photoactivity. Usually, larger surface area means much more active sites, at which the photocatalytic reaction occurs. Thus, as shown in Table 1, PbSnO3nanostructures with larger surface areas as 68 m2/g for nanoparticles and 50 m2/g for nanotubes, respectively, resulted in enhanced photocatalytic activities than bulk material with 10 m2/g of surface area. Meanwhile, the improved crystallinity of PbSnO3nanostructures (shown in XRD patterns) resulted in the increase of photocatalytic activity since it could reduce electron-hole recombination rate.
The wavelength dependence of the rate of acetone evolution from IPA degradation over PbSnO3 nanoparticles was investigated by using different cutoff filters, as shown in Fig. 7. The intensity variation of the incident light with different cutoff filters is given as an inset figure for reference. It is notable that the rate of acetone evolution decreased with increasing cutoff wavelength, which is in good agreement with the UV–Vis diffuse reflectance spectra of PbSnO3 nanoparticles, indicating the present reaction is driven by a visible light absorption. The used catalysts were again checked by XRD and UV–Vis reflectance spectroscopy to explore the stabilities of samples. There was no detectable change between the spectra of PbSnO3 before and after the photodegradation of IPA gas, suggesting that the catalyst was fairly stable for the degradation of organic compounds. For many p-block metal oxides photocatalysts with d10 configuration, the VB and CB are the 2p orbital of the oxygen atom and the lowest unoccupied molecular orbital (LUMO) of p-block metal center, respectively [22-24]. Meanwhile, for the lead-containing compounds, it was found that an additional hybridization of the occupied Pb 6s and O 2p orbitals seems to push up the position of the valence band and result in a narrower band gap . Based on the above depiction, we assumed that the VB of PbSnO3 is composed of hybridized Pb 6s and O 2p orbitals, whereas the CB is composed of Sn 5s orbitals, and these bands meet the potential requirements of organic oxidation.
Figure 7. Wavelength dependence of acetone evolution from isopropanol photodegradation on the cutoff wavelength of incident light, and UV–Vis diffuse reflectance spectrum of PbSnO3samples. The inset shows the wavelength dependence of light intensity with different cutoff filters (catalyst: 0.1 g, 300 W Xe lamp, 400 nm < λ < 500 nm)
In summary, we have successfully synthesized pure phase PbSnO3nanoparticles and nanotubes from the facile hydrothermal process at low temperature. The surfactant PVP used as the capping reagent plays a crucial role in the formation of tubular PbSnO3structure. PbSnO3nanostructures with better crystallinity and larger surface areas show enhanced photocatalytic activity for the decomposition of organic pollutant isopropanol under the visible light irradiation than the catalyst prepared by the solid-sate method.
This work was partially supported by the Global Environment Research Fund from the Ministry of Education, Culture, Sports, Science and Technology (MEXT) of the Japanese Government. This work was also supported the World Premier International Research Center Initiative (WPI Initiative) on Materials Nanoarchitectonics, MEXT, Japan and the Strategic International Cooperative Program, Japan Science and Technology Agency (JST).
Nature. 1972, 238:37.
COI number [1:CAS:528:DyaE38XltVykurw%3D]; Bibcode number [1972Natur.238...37F]Publisher Full Text
Nature. 1980, 286:474.
COI number [1:CAS:528:DyaL3cXmtVOgtrs%3D]; Bibcode number [1980Natur.286..474K]Publisher Full Text
Chem. Rev.. 1995, 95:69.
COI number [1:CAS:528:DyaK2MXjtF2qur4%3D]Publisher Full Text
Environ. Sci. Technol.. 2003, 37:2310.
COI number [1:CAS:528:DC%2BD3sXivFagsb8%3D]Publisher Full Text
Langmuir. 2004, 20:5865.
COI number [1:CAS:528:DC%2BD2cXkslWhtL0%3D]Publisher Full Text
Chem. Rev.. 1993, 3:341. Publisher Full Text
Nature. 2001, 414:625.
COI number [1:CAS:528:DC%2BD38XjtVyj]; Bibcode number [2001Natur.414..625Z]Publisher Full Text
J. Phys. Chem. B. 2001, 105:6061.
COI number [1:CAS:528:DC%2BD3MXkt1eku74%3D]Publisher Full Text
J. Photochem. Photobiol. Chem.. 2002, 148:85.
COI number [1:CAS:528:DC%2BD38Xktlaqtbk%3D]Publisher Full Text
J. Phys. Chem. B. 2005, 109:22432.
COI number [1:CAS:528:DC%2BD2MXhtFaltbnO]Publisher Full Text
J. Phys. Chem. B. 2006, 110:13829.
COI number [1:CAS:528:DC%2BD28XmtF2qs7g%3D]Publisher Full Text
Adv. Funct. Mater.. 2006, 16:2163.
COI number [1:CAS:528:DC%2BD28Xht1WhtLvK]Publisher Full Text
Chem. Mater.. 2007, 19(18):4585.
COI number [1:CAS:528:DC%2BD2sXptVaqu78%3D]Publisher Full Text
Chem. Mater.. 2008, 20:3809.
COI number [1:CAS:528:DC%2BD1cXmt1yntrs%3D]Publisher Full Text
Nature. 1992, 358:220.
COI number [1:CAS:528:DyaK38Xls1akt7w%3D]; Bibcode number [1992Natur.358..220E]Publisher Full Text
Chem. Lett.. 2006, 35:350.
COI number [1:CAS:528:DC%2BD28XktVCmtL8%3D]Publisher Full Text
Science. 1995, 269:966.
Bibcode number [1995Sci...269..966C]Publisher Full Text
Nature. 1998, 295:336. Publisher Full Text
Nano Lett.. 2007, 7:2142.
COI number [1:CAS:528:DC%2BD2sXms1equ7Y%3D]Publisher Full Text
Adv. Mater.. 2004, 16:1023.
COI number [1:CAS:528:DC%2BD2cXlslehsbk%3D]Publisher Full Text
Adv. Funct. Mater.. 2003, 13:639.
COI number [1:CAS:528:DC%2BD3sXms1Wltrc%3D]Publisher Full Text
J. Catal.. 1988, 113:72.
COI number [1:CAS:528:DyaL1cXlvVShs7Y%3D]Publisher Full Text
Catal. Lett.. 2002, 78:23.
COI number [1:CAS:528:DC%2BD38XktVGnsLs%3D]Publisher Full Text
Environ. Sci. Technol.. 2001, 35:2381.
COI number [1:CAS:528:DC%2BD3MXjtFalu7Y%3D]Publisher Full Text
J. Solid State Chem.. 2006, 179:1214.
COI number [1:CAS:528:DC%2BD28XisF2rsLY%3D]; Bibcode number [2006JSSCh.179.1214K]Publisher Full Text