The morphology and structure of the synthesized products are shown in Fig. . From the typical SEM image of the obtained products shown in Fig. , we can see that uniformly spherical particles with a diameter of 100 nm were obtained in the experiment, and no particles with other shape were found. A magnified SEM image reveals the detailed morphology, as shown in the inset of Fig. , which indicates that as-synthesized spheres were composed of fine nanocrystallites, with a rough surface and maybe have pores in it. The porous hollow structure was further investigated by the TEM image as shown in Fig. , and the intensive contrast between center and edge of the spheres indicates the formation of hollow structure in the final products, and the shell thickness of the spheres is about 20–25 nm. The bright spots scattered in the dark shell also confirm that the shell is porous. The crystal structure of the TiO2 sample was determined by XRD analysis as shown in Fig. . All the diffraction peaks can be well indexed to anatase phase of TiO2 (JCPDS 71-1169). No peaks of impurities were detected in the XRD patterns, indicating the high purity of the products. The strong and sharp peaks also confirm the well crystallization of the synthesized products.
a SEM image, b TEM image, c XRD patterns, d Nitrogen absorption–desorption isotherms and corresponding pore size distribution of TiO2 hollow spheres synthesized at 180°C for 48 h
Figure gives the nitrogen adsorption–desorption isotherms and corresponding pore size distribution of the TiO2
product. The isotherm shown in the Fig. can be well classified as type IV isotherm, indicating the formation of a typical porous structure [23
]. The corresponding pore size distribution (the inset in Fig. ) was calculated by means of Barret–Joyner–Halenda (BJH) method. From the distribution curve, we can see that porous TiO2
hollow spheres possess a broad pore size distribution due to the coexistence of mesoporous and micropores, but the pores with diameter of 1~3 nm are dominant in the final products. The BET analysis confirms the high specific surface area (132.5 m2
/g) of the product, which comes from the formation of the porous hollow structures.
In order to explore the evolution process of the porous hollow structure, time-dependant experiments were conducted, and Fig. gives the TEM images of products obtained at different reaction times. At the beginning of the hydrothermal reaction, titanium dioxide crystallized gradually and formed lots of small nanocrystallites. At the same time, NH4
was decomposed to NH3
at heating condition. These gas bubbles and TiO2
nanoparticles tend to aggregate together to minimize the interfacial energy, and the spherical aggregates are then formed by aggregation of original nanocrystallites nucleated on the gas–liquid interface as shown in Fig. . The solid aggregates then followed by a solid core evacuation and a hollowing effect are observed for those with a longer reaction time of 24 h (Fig. ), which is due to the continuous outward growth of the fine nanocrystallites and the gas bubbles gathered in the center of spheres [24
]. As the reaction time further increased, the migration sustainedly carried out to a certain degree, and the hollow sphere structure was obviously obtained (Fig. ). Based on the experimental results and analysis, the formation mechanism of hollow structure can be interpreted as the Ostwald ripening process [21
]. After the formation of the hollow spheres, lots of gas bubbles still existed in the shell, and they acted as templates for the formation of the loose packed shell. Thus, the hollow TiO2
spheres with a porous shell were finally obtained. XRD analyses reveal the different crystalline phases of products obtained at different reaction times, typically are amorphism, brookite and anatase. Accordingly, porous TiO2
spheres with different phases could be well controlled by adjusting the reaction time in our experiments.
TEM images of products obtained at different reaction times: a 0 h, b 24 h and c 48 h. Scalebar 50 nm
To investigate the adsorption property of synthesized products, 0.1 g of sample was added into 100 mL of aqueous methylene blue (MB) solution with different concentrations, and then the mixture was placed in the darkroom under magnetic stirring for 10 s. The adsorption property of the product for MB was measured by the MB concentration change before and after adsorption. The concentration of MB was detected using an UV–vis spectrophotometer. The color change of the MB solution (100 mg/L) after adsorption was shown in Fig. . The color contrast of the MB solution before and after adsorption indicates the excellent adsorption ability of the porous TiO2
hollow spheres for organic dyestuff. The test results of adsorption property of the sample to MB were shown in Table . The adsorption rate and adsorption quantity are calculated by the Eqs. 1 and 2, respectively.
The color contrast of 100 mg/L MB solution before and after adsorption. The left shows the primary solution, and the right is the solution after adsorption by the porous TiO2 sample for 10 s
The adsorption property test results of the TiO2 hollow sphere product
(Here, μ is the adsorption rate; q is the adsorption quantity; c0 and c are MB concentrations before and after mixing, respectively; A0 and A are absorbencies of the MB solution before and after mixing, respectively; V is the volume of the solution, and m is the mass of TiO2 sample.)
From the Table , it can be seen that 96~98% of MB in the solution can be adsorbed by the TiO2 sample at a low MB concentration of 50 and100 mg/L. When the concentration of MB increases to 200 mg/L, the adsorption quantity of the sample is up to 170.9 mg/g. The adsorption quantity has no obvious increase when the concentration of MB further increases (400 mg/L), which indicates the saturated adsorption quantity of the sample is about 171 mg/g. The high adsorption ability of this product indicates that the porous TiO2 hollow spheres may be used as adsorbent in some fields such as wastewater treatment.
As the synthesized TiO2 hollow sphere powder has a high specific surface area and intense adsorption ability, it is natural to consider its application in specific gas detection. The gas sensor was assembled using thin film prepared from the porous TiO2 hollow sphere powder. Figure – gives the typical isothermal response curves of the thin film sensor exposed to methanal (HCHO) gas at different operating temperatures (200, 300 and 400°C). In the gas-sensing test, HCHO gas was diluted in water vapor, and the flow velocity of the mixed gas was controlled at 0.6 L/min. The sensor sensitivity was defined as the slope of the Ra/Rg versus c curve, and herein, Ra is the resistance value of the sensor in clean air, Rg is the resistance value of the sensor in specific gas under test and c is the HCHO gas concentration.
Response curves to HCHO at a 200°C, b 300°C, c 400°C and d the response magnitude, Ra/Rg versus HCHO gas concentration
Based on the isothermal response curves, it can be concluded that the resistance value of the sensor decreases sharply when the HCHO gas passes the sensor, which indicated the good response speed of fabricated gas sensor. As time increases, gas diffusion slows down in the film, leading to a corresponding slowdown of the resistance decrease rate, resistivity finally reaching stability. When the analyte is removed, the resistance value rises immediately and restores fast. In general, it is believed that the sensing mechanism includes two reactions [25
]. First, oxygen adsorbed on the TiO2
sample surface captures electrons from TiO2
and transforms into Oad−
. Then, in the reductive gas condition (here is methanal), Oad−
will be reduced and its electron is given back to TiO2
, leading the electron density to increase. Therefore, in macro-view, when the thin film sensor is exposed to HCHO, the resistance value will decrease, and the relative change of the values at different gas concentrations is used to characterize gas sensitivity. Figure shows the curve of sensor-normalized resistivity (Ra/Rg
) versus HCHO gas concentration at different operating temperatures. It can be clearly seen that the gas sensor at operating temperature of 200°C presents a much higher gas-sensing property than the ones operated at 300 and 400°C. In addition, the sensor shows a relatively linear dependence on the HCHO concentration at 200°C, and the fitting line equation with the correlation coefficient of 0.9914 is as follows:
Up to now, few papers about TiO2
hollow spheres applied in gas sensing are reported. Moreover, the nanoscale TiO2
materials with other morphologies do not exhibit very good gas sensitivity, and the operating process needs to be conducted in a higher temperature condition [27
]. Compared to previous reported TiO2
samples, our porous TiO2
hollow spheres have a good performance in gas sensing at lower operating temperature. This satisfactory gas sensitivity attributed to the porous structure and large specific surface area indicates the importance of the microstructure control of gas-sensing layers.