- Nano Express
- Open Access
Capability of coupled CdSe/TiO2 heterogeneous structure for photocatalytic degradation and photoconductivity
© Zhang et al.; licensee Springer. 2014
- Received: 3 October 2014
- Accepted: 13 November 2014
- Published: 26 November 2014
Highly ordered TiO2 nanotube arrays (TiO2-NTAs), with a uniform tube size on titanium substrate, were obtained by means of reoxidation and annealing. A composite structure, CdSe quantum dots@TiO2 nanotube arrays (CdSe QDs@TiO2-NTAs), was fabricated by assembling CdSe quantum dots into TiO2-NTAs via cyclic voltammetry electrochemical deposition. The X-ray diffractometer (XRD), field-emission scanning electron microscope (SEM), and transmission electron microscope (TEM) were carried out for the determination of the composition and structure of the tubular layers. Optical properties were investigated by ultraviolet-visible spectrophotometer (UV-Vis). Photocurrent response under visible light illumination and photocatalytic activity of samples by degradation of methyl orange were measured. The results demonstrated that the photo absorption of the composite film shifted to the visible region, and the photocurrent intensity was greatly enhanced due to the assembly of CdSe QDs. Especially, photocurrent achieved a maximum of 1.853 μA/cm2 after five voltammetry cycles of all samples. After irradiation under ultra violet-visible light for 2 h, the degradation rate of composition to methyl orange (MO) reached 88.20%, demonstrating that the CdSe QDs@TiO2-NTAs exhibited higher photocatalytic activity.
- TiO2 nanotubes
- CdSe quantum dots
- Cyclic voltammetry
Very recently, highly ordered TiO2 nanotube arrays (TiO2-NTAs), which were synthesized by anodic oxidation on titanium substrate, had attracted great attention in recent years for solar cells , photocatalysis , water photoelectrolysis , and so on. However, due to its wide band gap of TiO2 (Eg = 3.2 eV ), only ultraviolet (UV) region with the wavelength below 390 nm of the solar spectrum can be utilized, which prevents its potential application. Therefore, much effort has been dedicated to expanding the photocatalytic function of the TiO2-NTAs to the visible light region . Quantum dot-sensitized solar cells (QDSSCs) are renowned energy devices known in the past decade for their distinct qualities, including absorb light in the visible region, simplicity in fabrication, tunable band gaps , and low cost. Of particular interest are CdX (X = S [7, 8], Se , and Te ) QDs, which have small and size-dependent band gaps and thus provide new opportunities for harvesting light energy in the visible and infrared regions of solar light [11–13].
It has been noticed that TiO2-NTAs anodized only after chemical polishing were of various lengths and able to show the blocked nanotube mouth, which prevents the continued investigation, such as sensitization by QDs. To solve this issue, a simple method to obtain uniform and highly ordered TiO2-NTAs via reoxidation has been developed in the present study, which similar with our previous work . Followed by annealing process, CdSe QDs were assembled onto the crystallized TiO2-NTAs by cyclic voltammetry at different cycles in a conventional three-electrode cell using an electrochemical workstation. The microstructure, composition, optical activity, and photocatalytic effect of CdSe QDs@TiO2-NTAs were investigated systematically.
Preparation of TiO2 nanotubes (NTAs) and decoration
Ti foils (99.6% purity, 0.2 mm) were divided through wire-electrode cutting into 1 × 2 cm2, then cleaned ultrasonically in acetone, alcohol, and de-ionized (DI) water for 5 min in turn. Chemical polishing was adopted to remove impurities adhered to the surface of Ti foils. The polishing solution consists of hydrofluoric acid (HF, AR), nitric acid (HNO3, AR), and de-ionized (DI) water, with the volume ratio of 1:1:2. At last, cleaned Ti foils were dried in nitrogen stream. The TiO2-NTAs were synthesized in a two-electrode cell containing a cathode of platinum foil at 60 V with weak magnetic stirring. The electrolyte was composed of 0.3 wt.% of NH4F (96% purity, AR), glycol (>99% purity, AR), and 2 vol.% of DI water, similar to previous investigation described by Grimes et al. . After 4 h of anodization, the samples were sonicated in DI water and carbinol (>99.5% purity, AR), respectively, and then dried by a drying oven to take off the first TiO2-NTAs films from substrate. Followed by cleaning, the reoxidation was carried out at ‘bowl-like’ Ti foil substrate at the same voltage and lasted for the same time. The above process has always been under room temperature. Before the CdSe sensitization, a subsequent heating at 350°C for 2 h with a temperature ramp rate of 2°C ⋅ min-1 in air was applied to achieve the crystallized TiO2-NTAs.
Synthesis of CdSe@TNAs
CdSe QDs were fabricated onto the TiO2-NTAs by cyclic voltammetry. Electrodeposition of CdSe QDs@TiO2-NTAs was performed in a conventional three-electrode cell using a Chi660D electrochemical workstation (Cheng Hua Instruments, Inc., Shanghai, China). The working electrode, the counter electrode, and the reference electrode were TiO2-NTAs after calcined at 350°C, a Pt foil and a saturated calomel electrode (SCE, filling solution is KCl of 3.5 mol/L), respectively. The electrolyte solution was prepared by mixing 0.25 M CdSO4, 0.25 M HNO3, and 0.015 M Na2SeO3 at ambient temperature using cyclic voltammetry technique, sweeping the potential between 0 and -1 V (vs. SCE) at a sweep rate of 0.1 V/S for different number of cycles (marked as ‘r’ in the Figures). CdSO4, HNO3, and Na2SeO3 were obtained from Sinopharm Chemical Reagent Co., Ltd., Shanghai, China. All reagents used were analytical grade. After electrochemical deposition, the samples were thoroughly rinsed by DI water and annealed at 350°C in vacuum atmosphere for 2 h. The samples were noted as r0, r3, r5, r7, and r9 according to the cycles of cyclic voltammetry (0, 3, 5, 7, and 9 times, respectively).
Characterizations and measurements
The surface morphology and thickness of TiO2-NTAs films were characterized by field-emission scanning electron microscope (SEM, Hitachi, S4800; Hitachi Ltd., Chiyoda-ku, Japan) and high-resolution transmission electron microscopy (HRTEM, JEM-2100; JEOL Ltd., Akishima-shi, Japan). Microstructures of TiO2-NTAs were conducted by X-ray diffractometer (XRD, MAC, M18XHF, Shimadzu, Kyoto, Japan) employing CuKα radiation. The absorption spectra of samples were recorded by an ultraviolet-visible (UV-Vis) spectrophotometer (UV-2550, Shimadzu, Kyoto, Japan) within the wavelength range of 300 to 900 nm.
The photoresponse characteristics of CdSe QDs@TiO2-NTAs heterostructures were evaluated by electrochemical workstation (CHI600D) in a photoelectron chemical cell under intermittent visible light illumination (100 mW/cm2 AM 1.5) with 0 V bias potential (vs. SCE) in 0.5 M Na2SO4 aqueous solution. Photocurrents were investigated in a three-electrode system under visible light illumination.
At last, the CdSe QDs sensitized TiO2-NTAs were employed as photocatalyst for the degradation of methyl orange (MO) and compared with pure TiO2-NTAs under UV lamp irradiation. The experiment was performed in a glass container. The samples were immersed in 10 mL ⋅ 15 ppm MO solutions and were irradiated with a 36 W high-pressure mercury lamp, which emits visible light of 404.7, 435.8, 546.1, 577.0, and 579.0 nm, and ultraviolet light of 365 nm. The distance between the sample and the high-pressure mercury lamp was 5.0 cm. The transmittance of the MO solution was measured at intervals of 10 min, and the total irradiation time is 120 min.
The CdSe QDs@TiO2-NTAs heterostructures show evident lager photocurrent under visible light irradiation than bare TiO2-NTAs. This is because that CdSe is a narrowband gap semiconductor, which greatly improved the production and separation of photoinduced electrons and holes. The excited electrons in the conduction band of CdSe could be easily transferred to the conduction band of TiO2 and further to photocurrent collector (Ti substrate) through the highly ordered TiO2-NTAs structure with well crystalline nature . Meanwhile, the photoexcited holes still stayed in the valence band of CdSe and were further transferred to the electrolyte, which benefit to restraining the recombination of photogenerated electrons and holes. Moreover, the reproducible and stable photoresponses are attributed to the existence of a good CdSe-nanotube interface that allows efficient electron injection from CdSe to TiO2-NTAs . The CdSe QDs@TiO2-NTAs sample prepared after five cycles showed a maximum photocurrent value of 1.853 μA/cm2. However, when the cycles further increased to 7 times and 9 times, the photocurrent of samples exhibited obviously decreased. It is because the CdSe nanoparticles became aggregated to form nanoclusters as the cycles increased, as shown in the SEM results. For the aggregated CdSe, particles may serve as the recombination centers of photoinduced electron-hole pairs at this circumstance and cannot inject electrons into the TiO2-NTAs network as effectively as smaller amount of CdSe nanoparticles, which greatly hindered the separation efficiency of the excited electron-hole pairs [18, 19].
Especially, photocurrent achieved a maximum of 1.853 μA/cm2 after five voltammetry cycles of all samples.
Degradation efficiency of CdSe@TiO 2 -NTAs thin films prepared at different cycle after UV irradiation for 2 h
Degradation efficiency (%)
where C0 represents the initial concentration, C t represents the concentration after t min reaction; A0 represents the initial absorbance, and A t represents the absorbance after t min reaction of the MO at the characteristic absorption wavelength of 464 nm. k α is the apparent first-order rate constant.
As its morphology shown in Figure 3, the sample of 5r has open nanotube top compared with other specimen. This morphology meant once photons entered into the nanotube, it can be multiple scattered with CdSe quantum dots and TiO2-NTAs, that is, the sample of 5r can utilize the photons more efficiently, especially the visible light. This conclusion can be confirmed by the UV-Vis diffuse reflection absorbance spectra (Figure 4) and photocurrent-time profiles (Figure 5). On the other hand, quantum size effect of CdSe QDs plays a crucial role in enhancing photocatalytic activities of CdSe QDs@TiO2-NTAs, which can be verified by UV absorption spectrum. Meanwhile, large grain sizes of bulk CdSe will lead to deficient contact between CdSe and TiO2-NTAs and weak interactions. These results are in accordance to the SEM results.
In summary, the uniform and highly ordered TiO2-NTAs films were obtained via reoxidation. The phase of TiO2-NTAs transforms to anatase phase under 350°C; it is shown that the CdSe covered both inner and outer wall of TiO2-NTAs efficiently through five cycles voltammetry electrochemical deposition. Size and distribution of CdSe nanoparticles were controlled by changing the electrodeposition cycles. Compared with the bare annealed TiO2-NTAs, the photo absorption of the composite film shifted to the visible region around 500 to 700 nm with the increase of the number of quantum dots, and the photocurrent intensity was greatly enhanced due to the assembly of CdSe QDs. Especially, photocurrent achieved a maximum of 1.853 μA/cm2 after five voltammetry cycles. Besides, the degradation rate of MO still reached their maximum value of 88.20% under UV lamp irradiation for 2 h. The enhanced ability makes this type of CdSe QDs@TiO2-NTAs promising applications in photo electrode for solar cells and photocatalyst candidate.
This work is supported by the National Natural Science Foundation of China (No. 51272001, 51102072 and 51472003), the State Key Program for Basic Research of China (2013CB632705), and the National Science Research Foundation for Scholars Return from Overseas, Ministry of Education, the Science Foundation for The Excellent Youth Talents of Chuzhou University (2013RC007) and Innovation Entrepreneurship Training Program for College Students of Chuzhou University (2014CXXL036), China. The authors would like to thank Yonglong Zhuang and Zhongqing Lin of the Experimental Technology Center of Anhui University for electron microscope test and discussion.
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