Constructing and Photocatalytic Performance of Flower-like CeO2/TiO2 Heterostructures

Hong-Xia WANG Xin-Xing LI Yu ZHOU

Citation:  Hong-Xia WANG, Xin-Xing LI, Yu ZHOU. Constructing and Photocatalytic Performance of Flower-like CeO2/TiO2 Heterostructures[J]. Chinese Journal of Inorganic Chemistry, 2022, 38(1): 127-136. doi: 10.11862/CJIC.2022.010 shu

花状CeO2/TiO2异质结的构筑及光催化性能

    通讯作者: 王红侠, hongxia0816@163.com
  • 基金项目:

    江苏省高等学校自然科学研究项目 19KJB430036

    江苏省高端结构材料重点实验室开放基金资助项目 hsm1907

    宿迁市科技计划项目 K202006

    宿迁学院新型复合材料研究创新团队 2021td01

摘要: 采用溶剂热法制备了三维花状CeO2/TiO2异质结光催化剂,然后以甲基橙(MO)为模拟有机污染物,在氙灯照射下考察了其光催化活性。结果表明,花状结构由纳米片和纳米颗粒复合而成,纳米片上均匀地附着CeO2颗粒。Ce/Ti的物质的量之比(nCe/nTi)和溶剂热时间影响异质结的光催化性能,当nCe/nTi=0.1、溶剂热时间为6 h时,CeO2/TiO2的光催化活性达到最佳,氙灯照射50 min的降解率达95%,光催化活性优于纯TiO2,这主要是CeO2和TiO2形成了异质结,有利于光生电子和空穴的分离。

English

  • Photocatalytic technology can be used to simulate natural photosynthesis, which can change solar energy into chemical energy, and degrade organic pollutants in sewage into harmless substances such as CO2 and H2O under normal temperature and pressure[1-3], thus avoiding the secondary pollution problem with traditional methods. TiO2 is an n-type semiconductor catalyst that is non-toxic, highly active, chemically stable, cheap, environmentally friendly, and it has been widely studied as an ideal photocatalyst[4-7]. However, in the process of photocatalysis, TiO2 has some defects, such as low quantum efficiency, easy recombination of electron - hole pairs, and low utilization of sunlight, which greatly restricts its extensive industrial application. The solution to these problems depends on in - depth and systematic basic research.

    To improve the photocatalytic activity of TiO2, the researchers used a variety of methods, such as controlling the morphology[8-11], doping transition metal ions and non - metallic ions[12-16], surface sensitization[17-18], semiconductor composite[19-20]. Recent studies show that the selection of semiconductors with appropriate energy bands to couple with TiO2, such as Bi2WO6[21-22], g-C3N4[23-25], CdS[26-27], CeO2[28-29], is conducive to separating electrons and holes, and improving the visible light catalysis of TiO2. CeO2 has high conductivity, thermal stability, oxygen storage capacity, and has a narrow energy gap (2.92 eV). Moreover, Ce4+ and Ce3+ ions are easy to reciprocal transformation, which makes CeO2 have good electron transfer ability and light absorption ability. The bandgap difference between TiO2 and CeO2 can promote the separation of photogenerated electronhole pairs and improve catalysis activity[30]. Although TiO2 and CeO2 composite materials have received extensive attention, the research of CeO2/TiO2 as promising photocatalytic materials is not deep enough. In particular, the photocatalytic efficiency of CeO2/TiO2 is far from practical application. Therefore, it is necessary to further improve the photocatalytic performance of CeO2/TiO2 by optimizing the experiment. In this work, we prepared CeO2/TiO2 photocatalyst materials with a three-dimensional flower structure by solvothermal method. Under xenon lamp irradiation, flower-like CeO2/TiO2 photocatalyst had high activity for methyl orange degradation.

    Preparation of CeO2: All the chemical reagents were chemically pure and were used directly without further processing. The water used was distilled water. Under strong stirring, 0.26 g cerium nitrate was dissolved in 100 mL water. After stirring frequently for 30 min, NaOH was added to the solution to control the pH to 9 - 10, followed by hydrothermal treatment at 180 ℃ in a Teflon-lined autoclave for 24 h. The product was centrifugally separated, washed with ethanol and distilled water, then dried. The sample was collected and then put into the annealing furnace at 500 ℃ for 2 h to obtain CeO2.

    Preparation of CeO2/TiO2: polyethylene glycol, cetyltrimethyl ammonium bromide, and carboxamide were immersed into 70 mL acetic acid solution, and after vigorous stirring to dissolve them, CeO2 was added into the above-mixed solution, finally added 2 mL butyl titanate by dropping and stirring for 20 min, and then moved the solution to 100 mL stainless steel autoclave lined with polytetrafluoroethylene. The reaction time was different at 150 ℃, and cooling with the furnace to room temperature. The precipitates were washed with ethanol and water thoroughly three times, drying at 80 ℃ and calcining at 450 ℃ for 1 h. According to the above preparation method, the samples prepared with Ce/Ti molar ratios nCe/nTi of 0.05, 0.1 and 0.2 in the reaction system were marked as 0.05CeO2/TiO2, 0.1CeO2/TiO2, 0.2CeO2/TiO2 respectively.

    Under the conditions of Cu target, 40 kV and 40 mA with Cu X-ray radiation source (λ=0.154 nm) and 2θ range of 20°-80°, the samples were recorded by X - ray diffractometer of Dandong Haoyuan instrument company; the morphologies of the synthetic samples were used by scanning electron microscope (SEM, Zeiss Merlin field emission) at the acceleration voltage of 5 kV; the specific surface area was measured using the measurement instrument (ASAP2460). The U-3900 ultraviolet - visible spectrophotometer with integrating sphere in Japan was used to measure the absorbance of powder. X -ray photoelectron spectroscopy (XPS) measurements were measured on an Escalab 250 Xi spectrometer. Photoluminescence (PL) spectra were measured using FLS 980 fluorescence spectrophotometer. The photocurrent response and electrochemical impedance spectroscopy (EIS) were carried by an electrochemical workstation (CHI660E).

    CeO2/TiO2 was added to methyl orange (MO) solution, then the MO solution was illuminated. The photocatalytic performance of the sample was tested by measuring the degradation rate of MO. The specific processes were listed as follows: 0.02 g of catalyst sample was added to 80 mL MO solution (10 mg·L-1), and ultrasonic agitation was performed for 30 min to achieve adsorption-desorption equilibrium in the dark. A 300 W xenon lamp was used to simulate and irradiate from the top of the MO solution. The xenon lamp was 10 cm away from the liquid surface. A small portion of the solution was taken every 10 min to be centrifuged and separated. The absorbance of the residual MO was analyzed by an ultraviolet-visible spectrophotometer.

    Fig. 1 shows the XRD patterns of CeO2/TiO2 heterojunction prepared by adding different amounts of CeO2. There were several different diffraction peaks of CeO2/TiO2 heterojunction nanoflowers at 2θ =25.3°, 37.9°, 48.1°, 54.1°, 55.2°, 62.6°, and 70.3° respectively, corresponding to anatase TiO2 (PDF No. 21 - 1272). The diffraction peaks with 2θ=28.6°, 33.2°, 56.6°, and 59.5° belong to the characteristic diffraction peaks of CeO2 (PDF No. 34 - 0394), indicating that the heterostructure nanocomposite composed of TiO2 and CeO2. It can be seen from the figure that the intensity of the diffraction peak of CeO2 increased gradually with the increase of CeO2 content.

    Figure 1

    Figure 1.  XRD patterns of CeO2/TiO2

    Fig. 2 showed that the prepared CeO2/TiO2 heterojunction had a three-dimensional flower-like structure, and nano-CeO2 particles adhered to the petals of TiO2. With the increase of CeO2 content, the number of CeO2 nanoparticles on the petals of TiO2 increased gradually.

    Figure 2

    Figure 2.  SEM and TEM images of (a, b) 0.05CeO2/TiO2, (c, d) 0.1CeO2/TiO2, and (e, f) 0.2CeO2/TiO2

    Solvothermal time can affect the morphology and properties of the samples. When the molar ratio of Ce and Ti was 0.1, and the samples were labeled as CeO2/TiO2-t, where t min was the reaction time. Fig. 3 shows that the diffraction peaks correspond to the characteristic diffraction peaks of TiO2 and CeO2 respectively.

    Figure 3

    Figure 3.  XRD patterns of (a) CeO2/TiO2-4, (b) CeO2/TiO2-6 and (c) CeO2/TiO2-12

    Fig. 4 shows the SEM images of CeO2/TiO2. It can be seen that under solvothermal conditions for 4 h, the CeO2/TiO2 heterojunction was a three-dimensional flower-like microsphere structure. The diameter of the microspheres was between 0.61 and 0.96 μm. The average diameter was 0.77 μm. The flower structure was formed by the directional aggregation of nanoparticles. When the reaction time increased up to 6 h, the diameter of the flower-like microspheres ranged from 0.58 to 1.29 μm, with an average diameter of 0.59 μm. When the solvothermal time was 12 h, the diameter of the three-dimensional flower-like structure was 0.88-1.89 μm, with an average diameter of 1.36 μm. CeO2 particles were oriented and integrated into a shuttle shape embedded between thin plates. With the increase of solvothermal time, the diameter of flower - like TiO2 became smaller at the beginning and larger at the next stage, and CeO2 gradually aggregated from nanoparticles to shuttle shape.

    Figure 4

    Figure 4.  SEM images of (a, b) CeO2/TiO2-4, (c, d) CeO2/TiO2-6 and (e, f) CeO2/TiO2-12

    Fig. 5 shows the N2 adsorption - desorption isotherms and BJH (Barrette - Joyner - Halenda) pore size distribution curves of samples. The Brunauer-EmmettTeller specific surface area (SBET), pore volume (VP), and average pore size of the samples are shown in Table 1. The results showed the prepared samples had high SBET and large VP, providing more active sites and light-harvesting capacity, and improving the utilization efficiency of light, thereby contributing to the degradation of organic pollutants.

    Figure 5

    Figure 5.  (a) N2 adsorption-desorption isotherms and (b) pore size distribution curves for CeO2/TiO2-t

    Table 1

    Table 1.  SBET, VP, and average pore diameter of CeO2/TiO2-t
    下载: 导出CSV
    Sample SBET / (m2·g-1) VP/ (cm3·g-1) Average pore diameter / nm
    CeO2/TiO2-4 159 0.41 8.68
    CeO2/TiO2-6 143 0.48 11.44
    CeO2/TiO2-12 110 0.36 11.48

    Fig. 6 shows the full spectrum of CeO2/TiO2-6 and the high-resolution XPS spectra of Ti2p, O1s, and Ce3d. It can be seen from Fig. 6a that the sample only contained C, O, Ti, and Ce elements. C was mainly derived from the residual carbon of some organic precursors during heat treatment and the oily carbon from the XPS instrument itself. The binding energies of 458.78 and 464.48 eV in Fig. 6b correspond to the characteristic peaks of Ti2p2/3 and Ti2p1/2 orbits respectively, which are the standard bond energies of Ti2p in pure TiO2, indicating that Ti exists in form of Ti4+ [31]. In the O1s spectrum of Fig. 6c, one peak at around 530.10 eV corresponds to the oxygen in the TiO2 lattice, and the other peak at around 531.58 eV corresponds to the hydroxyl (—OH) on the surface of TiO2[32-33]. In Fig. 6d, V (881.52), V″ (888.13), and V‴ (898.41) correspond to Ce3d5/2 spin-orbital bands; U (900.11), U″ (906.83), and U ‴ (915.81) correspond to Ce3d3/2 spin - orbital bands. The peaks labeled as V, V″, V‴, U, U″, and U‴ are attributed to the existence of Ce4+. The peaks at V' (885.13) and U' (903.12) are attributed to the presence of Ce3+ in the composite[34]. Ce3+ is mainly due to the strong interaction between TiO2 and CeO2, which makes Ce4+ reduced to Ce3+ [35].

    Figure 6

    Figure 6.  XPS spectra of CeO2/TiO2-6: (a) survey, (b) Ti2p, (c) O1s, (d) Ce3d

    Because the intensity of light emission depends on the recombination ability of excited electrons and holes, we can analyze the ability of semiconductor materials to capture and migrate photogenerated holes and electrons. The low intensity of the PL spectrum indicates that the recombination rate of electron - hole pairs is low and the separation efficiency of electron hole pairs represents reverse. Fig. 7 shows the PL spectra excited at 350 nm. The PL intensity of CeO2/TiO2-12 was lower than that of CeO2/TiO2-6, indicating that CeO2/TiO2-12 presented high separation efficiency.

    Figure 7

    Figure 7.  PL spectra of CeO2/TiO2-6 and CeO2/TiO2-12

    To investigate the photocatalytic activity of the sample, the photocatalytic degradation of MO (xenon lamp simulated sunlight) was carried out. The degradation rate of MO was calculated as follows: D=(1-A/A0)× 100%, where D is the degradation rate of MO solution; A0 is the absorbance of MO solution before irradiation; A is the absorbance of MO solution at the wavelength of 464 nm. The experimental results of photocatalysis under light were shown in Fig. 8.

    Figure 8

    Figure 8.  Photocatalytic degradation rate of MO for the samples

    Fig. 8a shows the curve of the photocatalytic degradation rate of MO under simulated sunlight for the samples prepared with various molar ratios of CeO2 and TiO2. Fig. 8b shows the photocatalytic degradation rate curves of MO under simulated sunlight irradiation for the samples prepared under different solvothermal times when the molar ratio of CeO2 to TiO2 was 0.1 (The material prepared without polyethylene glycol, cetyltrimethylammonium bromide, and carboxamide was recorded as CeO2/TiO2-B). It can be seen that the degradation rate of MO with catalyst increased with the extension of illumination time. The degradation rate of CeO2/TiO2 was better than that of TiO2 after 50 min illumination. The photocatalytic performance of flower like CeO2/TiO2 was higher than that of CeO2/TiO2 - B. 0.1CeO2/TiO2 had the best photocatalytic performance under 50 min illumination and the photocatalytic activity of CeO2/TiO2 - 6 was the best, and the degradation rate reached 95% after 50 min illumination (Fig. 8b). The degradation rate of MO solution added with pure TiO2 or CeO2 was only 78% or 70% respectively after 50 min illumination, which indicated that the composite of CeO2 and TiO2 enhances the photocatalytic activity of TiO2.

    Fig. 9 is the UV-Vis diffuse reflectance spectra of the samples. It can be seen that the absorption band edges of TiO2, CeO2, CeO2/TiO2 - 4, CeO2/TiO2 - 6, and CeO2/TiO2 - 12 were 393, 432, 463, 481, and 469 nm respectively. According to the formula Eg=1 240/λg (λg is absorption edge), the bandgaps (Eg) of TiO2, CeO2, CeO2/TiO2 - 4, CeO2/TiO2 - 6, and CeO2/TiO2 - 12 were about 3.16, 2.87, 2.68, 2.58, and 2.64 eV respectively, which indicates that CeO2/TiO2 broadens the absorption range compared with TiO2 and CeO2.

    Figure 9

    Figure 9.  UV-Vis diffuse reflectance spectra of the samples

    Fig. 10 shows the effects of reuse times of CeO2/TiO2 - 6 catalyst on photocatalytic activity. It can be seen that the degradation rates of MO by CeO2/TiO2-6 were 95%, 94%, and 92% respectively when the catalyst was reused for the first time, the second time, and the third time. The catalytic activity was not significantly reduced, indicating that the photocatalyst has certain stability and can be recycled many times.

    Figure 10

    Figure 10.  Effect of reuse degradation times of CeO2/TiO2-6 on the degradation rate of MO

    In the process of photocatalysis, water molecules or hydroxyl radicals can be oxidized by holes to generate hydroxyl radicals, and superoxide anion radicals may be generated when dissolved oxygen in water receives photogenerated electrons. Electron spin resonance (ESR) is generally used to detect hydroxyl radical (·OH) radical and superoxide radical (·O2-). Fig. 11 presents the ESR spectra of DMPO-·OH and DMPO·O2- obtained with 5, 5-dimethyl-1-pyrroline N-oxide (DMPO) as the radical scavenger. Under xenon lamp irradiation, the ESR spectra of ·OH showed four characteristic peaks, and that of ·O2- showed six characteristic peaks. However, there was no signal in the dark. It indicates that ·OH and ·O2- exist in the reaction system with CeO2/TiO2.

    Figure 11

    Figure 11.  ESR spectra of (a) DMPO-·OH and (b) DMPO-·O2- for CeO2/TiO2-6 in the dark and under xenon lamp irradiation

    The interface charge transfer and photogenerated charge recombination of the catalyst were investigated by electrochemical characterization. Fig. 12a shows the photocurrent response of the catalyst under xenon lamp irradiation. It suggests that CeO2, TiO2, and CeO2/TiO2-6 all had obvious photocurrent responses. When the light source was turned off, the current signal returned to the original level, and the response current of CeO2/TiO2-6 was higher than that of pure CeO2 or pure TiO2 under the light. Generally, the stronger the separation ability of photo-generated carriers, the stronger the photocurrent of the material. That shows the separation ability of CeO2/TiO2 - 6 photo - generated carriers was better than pure CeO2 and TiO2, which is mainly due to the formation of heterojunction between CeO2 and TiO2. EIS can further confirm the effective separation of photogenerated electrons and holes. The arc radius in EIS (Fig. 12b) is related to the charge transfer resistance of the material. In general, the smaller the arc radius, the faster the separation or transfer speed of photogenerated carriers, and the photocurrent intensity is also increased. It can be seen that CeO2/TiO2 - 6 had the smallest arc radius, which indicates that CeO2/TiO2 - 6 has the smallest electron transfer resistance and the best charge separation efficiency, which is consistent with the photocurrent response.

    Figure 12

    Figure 12.  (a) Transient photocurrent responses of CeO2, TiO2, and CeO2/TiO2-6; (b) EIS spectra of CeO2, TiO2, and CeO2/TiO2-6

    Fig. 13 shows the photocatalysis mechanism of CeO2/TiO2. Under simulated sunlight, CeO2/TiO2 can absorb not only ultraviolet light but also visible light. Both CeO2 and TiO2 can be excited by ultraviolet light, then the electrons jump to the conduction band to form the conduction band electron (e-) while leaving holes (H+) in the valence band. Because the conduction band (CB) of CeO2 is higher than that of TiO2, the electrons in CB of CeO2 transfer to CB of TiO2 through the interface. On the other hand, the valence gap (VB) of CeO2 is lower than that of TiO2, and the holes of VB of TiO2 are transferred to VB of CeO2, which is prone to the separation of photogenerated electron-hole pairs[30]. Under visible light irradiation, electrons from VB of CeO2 are transferred to CB of TiO2, and photogenerated electrons in CB of CeO2 can be transferred to CB of TiO2, thus inhibiting the recombination of photogenerated electrons and hole[36]. The results were consistent with the photocurrent response and EIS. Subsequently, the e- was reacted with the O2 to form ·O2-. The H2O could be oxidized by h+ to produce ·OH. The pollutant was oxidized by ·O2- and ·OH to produce CO2 and H2O. Simultaneously, the h+ in VB of CeO2 was directly involved in the oxidation of pollutants.

    Figure 13

    Figure 13.  Photocatalysis mechanism of CeO2/TiO2

    The three-dimensional flower-like CeO2/TiO2 heterojunction was prepared by the solvothermal method. Compared with TiO2, flower-like CeO2/TiO2 heterojunction showed better photocatalytic performance under simulated sunlight. Among them, the degradation rate of MO reached 95% when CeO2/TiO2-6 was illuminated for 50 min, and the photocatalytic performance reached the best. The flower-like CeO2/TiO2 heterojunction had excellent catalytic performance, which is mainly due to the following factors. First of all, the three - dimensional hierarchical structure, with a large specific surface area and a different size of pore structure, greatly improves the utilization of light. Secondly, the heterojunction effect can enhance the efficiency of charge separation and interface charge transfer greatly.


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  • Figure 1  XRD patterns of CeO2/TiO2

    Figure 2  SEM and TEM images of (a, b) 0.05CeO2/TiO2, (c, d) 0.1CeO2/TiO2, and (e, f) 0.2CeO2/TiO2

    Figure 3  XRD patterns of (a) CeO2/TiO2-4, (b) CeO2/TiO2-6 and (c) CeO2/TiO2-12

    Figure 4  SEM images of (a, b) CeO2/TiO2-4, (c, d) CeO2/TiO2-6 and (e, f) CeO2/TiO2-12

    Figure 5  (a) N2 adsorption-desorption isotherms and (b) pore size distribution curves for CeO2/TiO2-t

    Figure 6  XPS spectra of CeO2/TiO2-6: (a) survey, (b) Ti2p, (c) O1s, (d) Ce3d

    Figure 7  PL spectra of CeO2/TiO2-6 and CeO2/TiO2-12

    Figure 8  Photocatalytic degradation rate of MO for the samples

    Figure 9  UV-Vis diffuse reflectance spectra of the samples

    Figure 10  Effect of reuse degradation times of CeO2/TiO2-6 on the degradation rate of MO

    Figure 11  ESR spectra of (a) DMPO-·OH and (b) DMPO-·O2- for CeO2/TiO2-6 in the dark and under xenon lamp irradiation

    Figure 12  (a) Transient photocurrent responses of CeO2, TiO2, and CeO2/TiO2-6; (b) EIS spectra of CeO2, TiO2, and CeO2/TiO2-6

    Figure 13  Photocatalysis mechanism of CeO2/TiO2

    Table 1.  SBET, VP, and average pore diameter of CeO2/TiO2-t

    Sample SBET / (m2·g-1) VP/ (cm3·g-1) Average pore diameter / nm
    CeO2/TiO2-4 159 0.41 8.68
    CeO2/TiO2-6 143 0.48 11.44
    CeO2/TiO2-12 110 0.36 11.48
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  • 发布日期:  2022-01-10
  • 收稿日期:  2021-03-30
  • 修回日期:  2021-10-29
通讯作者: 陈斌, bchen63@163.com
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