Home Solution-processed Bi2S3/BiVO4/TiO2 ternary heterojunction photoanode with enhanced photoelectrochemical performance
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Solution-processed Bi2S3/BiVO4/TiO2 ternary heterojunction photoanode with enhanced photoelectrochemical performance

  • Xinli Li , Sha Wang , Kunjie Wang , Jiachen Yang , Kexuan Wang , Chao Han , Lihua Li , Renhong Yu and Yong Zhang EMAIL logo
Published/Copyright: May 24, 2023
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Nanotechnology Reviews
From the journal Nanotechnology Reviews Volume 12 Issue 1

Abstract

TiO2 is an important component of photoelectric devices. How to broaden the light absorption of TiO2 and accelerate the separation of photo-generated electrons and holes is the focus of the current research. Building heterojunction with narrow band gap semiconductor and TiO2 is one of the important measures to improve its photoelectric performance. We prepared BiVO4/TiO2 binary heterojunction by the simple hydrothermal method and analyzed the effect of BiVO4 precursor solution concentration on the microstructure and photoelectric performance of the heterojunction. BiVO4/TiO2 binary heterojunction can effectively improve the photoelectric performance of TiO2, and the transient current density reaches 85 μA/cm2. To further boost the photocurrent of BiVO4/TiO2, Bi2S3 was in situ grown on the heterojunction to form Bi2S3/BiVO4/TiO2 ternary heterojunction. The results show that the band gap of Bi2S3/BiVO4/TiO2 composites is significantly narrowed compared with that of TiO2. The light absorption has been expanded to the visible range, and the photogenerated current density is also greatly boosted (0.514 mA/cm2). This Bi2S3/BiVO4/TiO2 ternary heterojunction accelerates the separation of photo-carriers and improves the photoelectric performance of the device. The possible transport mechanism of photo-carriers in ternary heterojunction is analyzed. The current study provides an effective strategy for in situ construction of novel multicomponent heterojunction and provides a basis for the application of Bi2S3/BiVO4/TiO2 in the optoelectronic field.

Keywords: TiO2/BiVO4/Bi2S3 heterojunction; composite materials; photoelectric performance

1 Introduction

Due to the process of the economic development, the negative effects of the highly developed industry are not anticipated enough, and the prevention is not in place, resulting in a global energy crisis and environmental pollution [1]. Therefore, it is imperative to develop advanced technologies for environmental remediation, as well as energy storage and conversion [2]. Solar energy is one of the most potential clean energy, which has attracted wide attention [3], due to its abundance, cleanliness, security, and sustainability [4]. Solar cells are effective devices that can directly convert solar energy into electrical energy. Organic–inorganic hybrid perovskite thin film solar cells are the most potential photovoltaic devices. Photo-anode is the core part of thin film solar cells. Photo-anode materials mainly include SnO2, ZnO, and TiO2. Because of the wide band gap, these common photo-anode materials have low absorption and utilization of visible light. How to make the photoelectric performance better of these photo-anode materials is one of the research highlights.

Among these kinds of photo-anode materials, TiO2 has the following advantages: excellent physical and chemical stability, nontoxic, nonpolluting, and low cost, which is still the main research object of photo-anode materials. However, TiO2 has the defects of a wide band gap (about 3.2 eV) and electron-hole easy to recombination, which limit its optical and photoelectric properties. Therefore, TiO2 needs to be modified [5], such as semiconductor recombination [6], doping [7], surface modification [8], and other methods, which can improve the performance of TiO2, broaden the optical absorption range, restrain the recombination of electrons and holes, improve the separation of photo-generated carriers, and greatly raise the photoelectric conversion efficiency of devices. Among them, combing narrow band gap semiconductor and TiO2 to construct hetero-junction is the most widely used and effective method [9]. For example, Bi2S3, CdS, Cu2S, and so on, these narrow band gap semiconductors can be combined with TiO2 to build and form heterojunctions. In our previous researches [3,10,11,12], we prepared Bi2S3 nanomaterials and constructed TiO2/Bi2S3 heterojunction with TiO2. The results showed that the TiO2/Bi2S3 hetero-junction can effectively improve its photoelectric performance.

Bismuth-based semiconductors have attracted research interest, mainly because of their stable chemical properties, suitable band gap, low cost, and easy preparation. BiVO4 is a semiconductor material with properties such as good visible light driving activity, suitable band gap [13] (2.4 eV), low cost, splendid dispersion, nontoxic, and corrosion resistance [14,15]. The construction of hetero-junction between BiVO4 and TiO2 can widen the absorption range to visible light and promote the dissociation of electron–hole pairs. Wang et al. [16] prepared snowflake-shaped BiVO4 and TiO2 microspheres, obtained TiO2/BiVO4 Z-type hetero-junction through physical mixing, and used them for photocatalytic degradation of pollutants. Guo et al. [17] indicated that coupling BiVO4 with TiO2 by electrospinning enhances the photocatalytic degradation of rhodamine B dye. Khalil et al. [18] reported the role of exposed TiO2’s (001) and (101) facets on the performance of BiVO4/TiO2 photocatalytic fuel cells. At the same time, from the perspective of electronic structure, the hybridization of the 6 s orbital of Bi and the 2p orbital of O will cause the E VB to move up, which can accelerate the separation of electron and hole pairs in the process of electron transfer. On the basis of our previous research, we have learned that a single compound sensitizes TiO2, and its improved photoelectric performance is limited.

Co-sensitizers are promising materials that bring broader light absorption and an optimal cascade structure of energy level in quantum dots, leading to enhancing the charge transfer process and better photovoltaic performance than bare quantum dots [19]. Among many photosensitive materials, BiVO4 and Bi2S3 are potential photon-absorbing materials, which have the tendency to capture the visible photons in the solar spectrum. The bandgap of BiVO4 is 2.4 eV, and the bandgap of TiO2 is 3.2 eV. Due to the energy band difference, TiO2 and BiVO4 can construct an efficient hetero-junction and promote carrier separation [17]. BiVO4/TiO2 photo-catalysts were prepared and reported [16,17,18]. Likewise, Bi2S3 is an excellent light-absorbing material with the moderate band gap. For example, Han and Jia [20] prepared and used the 3D Bi2S3 nanosheet-modified TiO2 nano-rod array. It showed good photo-electrochemical properties and high charge transfer efficiency. Wu et al. [21] effectively deposited Bi2S3 nanoparticles on TiO2 nanotube arrays by sequential chemical bath deposition. The results of electro-chemical impedance spectroscopy and photoluminescence spectroscopy showed that the photo-generated electrons and holes of Bi2S3–TiO2 composites were effectively separated under visible light excitation, and their photo-catalytic performance was greatly improved compared with a single TiO2 nanotube. Annealing treatment on the Bi2S3/TiO2 can effectively improve its photoelectric properties [12].

To further promote the photoelectric performance of TiO2, we first prepared TiO2/BiVO4 binary heterojunction by the hydrothermal method, optimized the effect of the amount of BiVO4 precursor reactant on the heterojunction, and optimized the process parameters. On the basis of this heterojunction, Bi2S3 was in situ grown on BiVO4/TiO2 binary heterojunction by the hydrothermal method, and then the Bi2S3/BiVO4/TiO2 ternary heterojunction was formed. We optimized the hydrothermal growth time of Bi2S3. The experimental results show that the prepared Bi2S3/BiVO4/TiO2 heterojunction exhibits excellent photoelectric characteristics, and its transient photoelectric current is greatly improved. Finally, the transport mechanism of photo-generated carriers in Bi2S3/BiVO4/TiO2 heterojunction is analyzed.

2 Experimental

2.1 Materials

Fluorine-doped tin oxide (FTO) glass was used as the substrate (Luoyang Guluo Glass Co. Ltd.). Tetrabutyl titanate (C16H36O4Ti), concentrated hydrochloric acid (HCl), bisthum nitrate pentahydrate (Bi(NO3)3·5H2O), ethylene glycol (EG,(CH2OH)2), ammonium metavanadate (NH4VO3), and thiourea were of analytical grade. We did not further purify these chemicals.

2.2 Preparation of TiO2

The TiO2 materials were grown on the FTO substrate. The FTO was cleaned with acetone, absolute ethanol, and deionized water for 20 min by ultrasonic cleaning. A total of 15 mL of concentrated sulfuric acid and 15 mL of deionized water were mixed in a beaker. After uniform magnetic stirring, 0.5 mL of tetrabutyl titanate was added with a pipette gun, and magnetic stirring was continued for 40 min. The precursor solution was transferred to 50 mL polytetrafluoroethylene lining and placed into the reactor for the hydrothermal reaction, the reaction temperature is 150°C, and the reaction time is 12 h. After the reaction, the mixture is cooled to room temperature. The sample was taken out, washed alternately with deionized water and absolute ethanol, and dried at 60°C to obtain TiO2 nanorod arrays.

2.3 Preparation of BiVO4/TiO2 composite

BiVO4/TiO2 composite films were synthesized by the simple hydrothermal method. First, 3 mmol (1.455 g) of Bi(NO3)3·5H2O is weighed and dissolved in 25 mL of ethylene glycol under magnetic stirring, which is recorded as solution A. A total of 3 mmol (0.351 g) of NH4VO3 is dissolved in 15 mL of hot deionized water (60°C) by stirring using a magnetic stirrer, and the magnetic stirring is continued for 30 min until the solution is uniform. Then, solution B is added to solution A under stirring. At this time, the solution appears bright orange. Stirring is continued for 15 min to obtain the precursor solution for preparing BiVO4. The prepared TiO2 nanorod sample was placed into the polytetrafluoroethylene lining carefully in the conductive surface downward position at an angle of about 45°, and then the precursor solution prepared in advance is poured. The conductive glass about 1 cm long is placed without immersing in the solution. The hydrothermal reaction is conducted under the constant temperature of 120°C, and the reaction temperature is 10 h. The sample was cooled naturally to room temperature. After the reaction, the sample was rinsed with deionized water and dried to obtain BiVO4/TiO2 sample. In the process of hydrothermal preparation of nanomaterials, the precursor concentration is an important variable. So, during the BiVO4 growth, we set the reaction precursor concentration as 2, 3, and 4 mmol. For convenience, we marked the prepared samples BiVO4/TiO2 as VT (2 mmol), VT (3 mmol), and VT (4 mmol).

2.4 Preparation of Bi2S3/BiVO4/TiO2 composite

Bi2S3/BiVO4/TiO2 hetero-junction was also prepared by the hydrothermal method. A total of 1 mmol (0.076 g) of thiourea was weighed in an electronic balance and dissolved in 35 mL of deionized water through in situ conversion using thiourea as the sulfur source, and magnetic stirring was performed for 30 min. The conductive surface of the prepared BiVO4/TiO2 composite film sample was tilted downward and placed into the lining, and then the sample was poured into the prepared sulfur source solution, leaving about 1 cm of conductive glass not immersed in the solution. The hydrothermal reaction was carried out at 170°C for 1.5, 3, 5, and 7 h, respectively. At the end of the reaction, the sample was washed and dried with deionized water and absolute ethanol to obtain Bi2S3/BiVO4/TiO2 (BVT) heterostructure samples. The samples obtained are recorded as BVT (1.5 h), BVT (3 h), BVT (5 h), and BVT (7 h) according to the reaction time. Figure 1 shows the schematic of Bi2S3/BiVO4/TiO2 ternary heterojunction preparation process.

Figure 1 Schematic of Bi2S3/BiVO4/TiO2 hetero-junction preparation process.
Figure 1

Schematic of Bi2S3/BiVO4/TiO2 hetero-junction preparation process.

2.5 Characterization

The phase composition was characterized by X-ray diffractometer (D8 Advanced X, Brooke, Germany), using Cu Kα as a radiation source, the voltage set as 40 kV, the scanning speed set as 6°/min, and the 2θ range from 10 to 80°. The morphology and the structure of the samples were studied by field emission scanning electron microscopy (FESEM; JSM-7800F, Shimadzu Company, Japan) and high-resolution transmission electron microscopy (TEM; JEM-210, Shimadzu, Japan), and the X-ray photoelectron spectroscopy (XPS; Thermo Scientific K-Alpha) test is used to analyze the surface element state and the composition of composite materials. The optical absorption spectrum of the sample was characterized by ultraviolet-visible diffuse reflectometer (PerkinElmer Lambda1050, USA). The photoelectric characteristics of photo-anode materials were measured by the electrochemical workstation (CHI660E), including transient photocurrent and alternating current impedance (electrochemical impedance spectroscopy (EIS)). The test light source consisted of 350W xenon lamp and AM1.5G filter. The three-electrode test system includes reference electrode (Ag/AgCl electrode), counter electrode (platinum electrode), working electrode (photoelectric electrode), and Na2SO4 solution with 0.5 mol/L electrolyte.

3 Results and discussion

3.1 Characterization and analysis of BiVO4/TiO2 heterojunction

To obtain Bi2S3/BiVO4/TiO2 ternary hetero-junction photoelectric materials with excellent performance, we optimized the preparation process parameters of BiVO4/TiO2 binary heterojunction. Figure 2 displays the X-ray diffraction (XRD) patterns of BiVO4/TiO2 binary heterojunction prepared under different concentrations of BiVO4 precursors solution. The diffraction peak of the prepared TiO2 is relatively consistent with the standard PDF card 21-1276, which shows that the prepared TiO2 is rutile phase. These peaks located at 36.1, 62.9, and 69.8°, which are corresponding to the (101), (002), and (112) planes of the rutile phase TiO2. For the BiVO4, diffraction peaks are located at 18.9, 28.8, 30.5, 39.8, 42.3, and 53.3°, which correspond to the (011), (121), (040), (211), (150), and (161) planes (JCPDS No: 14-0688). The diffraction peak intensity of (121) and (040) planes increases with the BiVO4 precursor concentration increase, indicating that more and more BiVO4 materials were formed. These (121) and (040) crystal planes indicated the monoclinic phase BiVO4 appear.

Figure 2 XRD patterns of pure TiO2 and BiVO4/TiO2 composite thin films.
Figure 2

XRD patterns of pure TiO2 and BiVO4/TiO2 composite thin films.

Figure 3 shows the SEM images of TiO2 nanorod array and BiVO4/TiO2 composites (VT (2 mmol), VT (3 mmol), and VT (4 mmol)). Figure 3(a) shows the TiO2 nanorod array SEM image. The TiO2 nanorod array is very intuitive. These nanorods are evenly arranged and grown in the direction perpendicular to the conductive glass substrate, and no obvious defects can be seen. In addition, these nanorods are closely arranged with each other, presenting a rod-like array of quadrilateral structure, with good dispersion, and the top of the rod is relatively rough. The morphology of TiO2 nanorod array prepared in this work is consistent with that reported by Zhu et al. [22] and Serikov et al. [23]. The reason for the formation of this arrangement can be attributed to the fact that during the growth of TiO2 crystal nucleus under acidic conditions, the (110) crystal surface was first adsorbed by Cl–, and the growth rate of this crystal surface decreased, making TiO2 grow anisotropic along the [001] orientation. Figure 3(b)–(d) shows the SEM images of VT (2 mmol), VT (3 mmol), and VT (4 mmol), respectively. It is obvious that the peanut-like BiVO4 is attached to the TiO2 nanorod array. BiVO4 particles are evenly distributed. When the concentration of the precursor of the reactant continues to increase, the morphology of BiVO4 changes, showing a football shape with two ends. It shows that BiVO4/TiO2 heterojunction was successfully prepared at the low-temperature hydrothermal method with 120°C, which is consistent with the analysis conclusion of the XRD diagram.

Figure 3 SEM images of (a) pure TiO2, (b) VT (2 mmol), (c) VT (3 mmol), and (d) VT (4 mmol).
Figure 3

SEM images of (a) pure TiO2, (b) VT (2 mmol), (c) VT (3 mmol), and (d) VT (4 mmol).

To clarify the growth of BiVO4 on TiO2, we tested and analyzed the cross section of the BiVO4/TiO2 sample. Figure 4(a) shows the cross-sectional SEM image of BiVO4/TiO2. It can be seen that the TiO2 nanorods are aligned neatly and grown vertically on the FTO substrate. On the top of the TiO2 nanorods, there are small projections composed of scales. From the top view of SEM images (Figure 3(b–d)), we have learned that BiVO4 is a mulberry-shaped structure composed of multiple scales. Through comparative analysis, it can be inferred that the small protrusions observed in these sections are BiVO4. A line scan was carried out based on the cross-sectional SEM image of BiVO4/TiO2, and the results are shown in Figure 4(b). The yellow line in Figure 4(a) is the area where the line scan is performed in Figure 4(b). In the 0–2 μm range of line scan testing, the main elements are Na, O, Sn, and Si. Combining the SEM image of the cross section, it can be seen that this region mainly corresponds to the glass substrate and the FTO layer. Elements such as Na, Si, Sn, and O come from glass substrates and FTO. In the range of 2–5.5 μm, the main elements obtained are Ti and O, which corresponds to TiO2 nanorods. More than 5.5 μm is mainly composed of Bi, V, and O elements. These Bi, V, and O elements mainly come from BiVO4 nanomaterials. The results of these line scan results are consistent with those obtained by SEM and XRD analyses.

Figure 4 (a) SEM image of BiVO4/TiO2 cross section and (b) line scanning of selected areas in (a).
Figure 4

(a) SEM image of BiVO4/TiO2 cross section and (b) line scanning of selected areas in (a).

For this BiVO4/TiO2 binary heterojunction, it was characterized by TEM. Figure 5(a) shows the TEM image of the BiVO4/TiO2 composite film. We can see that there are mulberry-like substances on the TiO2 nanorods. This mulberry-like substance is BiVO4. Figure 5(b) shows the electron diffraction of the TiO2 nanorods. Comparing the d values and angle measured in Figure 5(b) with the XRD standard card (JCPDS 21-1276, I41/and space group, a = 3.785 nm), we found that the measured d values were consistent with the lattice plane spacing of (1–11) TiO2 and (–211) TiO2, and then the phase of TiO2 was confirmed. By using the same method, BiVO4 was also calibrated and confirmed. The results of TEM are consistent with the results of SEM, XED, and line scan.

Figure 5 (a) TEM image of BiVO4/TiO2, (b) the SAED of TiO2 image, and (c) the SARED of BiVO4.
Figure 5

(a) TEM image of BiVO4/TiO2, (b) the SAED of TiO2 image, and (c) the SARED of BiVO4.

Transient photocurrent response and electrochemical impedance are important parameters to evaluate the photo-electrochemical properties of photo-anode materials. Figure 6 shows the transient photocurrent diagrams and electrochemical impedance diagrams of BiVO4/TiO2 composites and TiO2 nanorod array. The generation and disappearance of photocurrent are analyzed and characterized by controlling the light source switch. When the light is irradiated on the heterojunction, the photocurrent will be generated instantaneously. When the light is turned off, the photocurrent returns to zero, which indicates that the electron–hole pairs generated by the light excitation are separated. The VT (3 mmol) composite shows the maximum photocurrent density (0.0825 mA/cm2), followed by VT (2 mmol) and then VT (4 mmol). The photocurrent response of the sample directly reflects the generation and transfer of photogenerated carriers [24]. Compared with pure TiO2 nanorod array samples, the photocurrent density of BiVO4/TiO2 heterojunction samples has been greatly improved. The photocurrent density of these BiVO4/TiO2 composites is relatively stable. It proves that the BiVO4/TiO2 can effectively separate the photogenerated electron–hole [25].

Figure 6 (a) Transient photocurrent responses and (b) electrochemical impedance spectra of BiVO4/TiO2 composites prepared with precursor solution different concentrations of BiVO4.
Figure 6

(a) Transient photocurrent responses and (b) electrochemical impedance spectra of BiVO4/TiO2 composites prepared with precursor solution different concentrations of BiVO4.

The interface transfer resistance of carriers in heterojunction can be analyzed by EIS. The EIS semicircle represents the interfacial charge transfer resistance of the sample. The greater the resistance, the greater the interface resistance, indicating the worse the performance of the sample. Therefore, the smaller the radius of curvature of the semicircle means the smaller the interface resistance of the sample, which proves that the smaller the electron loss during charge transmission, the higher the transmission efficiency, the lower the carrier recombination rate, and the better the photoelectric performance of the material. The VT (3 mmol) sample has the smallest radius of EIS curvature. The order of curvature radius from large to small is: pure TiO2 nanorods > VT (4 mmol) > VT (2 mmol) > VT (3 mmol). The results show that VT (3 mmol) sample is more conducive to the interface electron transfer, and the carrier recombination rate is lower. In general, VT (3 mmol) shows the best electrochemical performance for BiVO4/TiO2 heterojunction with different amounts of BiVO4.

3.2 Characterization and analysis Bi2S3/BiVO4/TiO2

Figure 7 shows the XRD patterns of Bi2S3/BiVO4/TiO2 heterojunctions prepared by the hydrothermal method with different hydrothermal time. The diffraction peak positions at 36.1, 62.9, and 69.8° match with the (101), (002), and (112) crystal planes of TiO2, which are in better agreement with the standard PDF#21-1276, and thus, the prepared TiO2 is known to be rutile. In the XRD pattern of the binary composite VT (see the VT curve in Figure 7(a)), there is an obvious diffraction peak at 18.9°, which matches with the standard PDF#14-0688 of BiVO4, corresponding to the (011) crystal plane of BiVO4, and after the growth of Bi2S3, the diffraction peak of BiVO4 at this point is not obvious, probably due to adhering of Bi2S3, which affects BiVO4 diffraction peak intensity. Moreover, the diffraction peaks at 28.8 and 54.6° are corresponding to the (121) and (013) crystal planes of BiVO4, respectively. Figure 7(b) is a partially enlarged view of Figure 7(a). The diffraction peaks of Bi2S3 match well with the standard PDF#17-0320, and the diffraction peak positions at 25.2, 33.9, and 45.7° match with the (310), (311), and (440) crystal planes of Bi2S3 in BVT (1.5 h), the diffraction peak at 25.2° is almost absent, presumably due to the short hydrothermal time and the low amount of Bi2S3 generated by conversion. In addition to this, some characteristic peaks of conductive glass SnO2 were observed. In this XRD pattern, the diffraction peaks corresponding to Bi2S3, BiVO4, and TiO2 can be found for the samples obtained at different hydrothermal times, indicating that the ternary photo-anode composites were successfully prepared.

Figure 7 (a) XRD patterns of different photo-anode materials. (b) Partial enlarged view of (a).
Figure 7

(a) XRD patterns of different photo-anode materials. (b) Partial enlarged view of (a).

Figure 8 displays the SEM images of TiO2, BiVO4/TiO2, and Bi2S3/BiVO4/TiO2 composite films. This rod-like TiO2 nanoarray is consistent with those reported by Zhu et al. [22] and Serikov et al [23]. The reason for the formation of this arrangement can be attributed to the preemptive adsorption of Cl− on the (110) crystal plane in the growth of TiO2 nuclei under acidic conditions, which reduces the growth rate of this crystal plane and makes TiO2 grow anisotropically along the [001] orientation [26]. Figure 8(b) shows the SEM image of BiVO4/TiO2 binary heterojunction. The peanut-like BiVO4 grains appeared on the basis of the original TiO2. Figure 8(c)–(f) shows the SEM images of Bi2S3/BiVO4/TiO2 heterojunctions prepared by growing Bi2S3 using different hydrothermal times of 1.5, 3, 5, and 7 h, respectively. In Figure 8(c)–(f), when the hydrothermal time is 1.5 h, the in situ transformation has grown long strips of Bi2S3, stacked together in a burr-like manner, but with little content. With the gradual increase of hydrothermal time, the content of Bi2S3 increased with the increase of hydrothermal time, and the content of long strips of Bi2S3 reached the highest at the hydrothermal time of 5 h, the grains were clear and evenly attached to the surface of BiVO4, and when the hydrothermal time was 7 h, the morphology of some Bi2S3 changed from long strips to short rods and flakes, which were closely piled up and covered up the BiVO4, which was difficult to observe. The tight structure between TiO2, BiVO4, and Bi2S3 further confirmed the successful preparation of Bi2S3/BiVO4/TiO2 heterojunctions using different hydrothermal times, which was consistent with the analytical conclusion of XRD plots. For the in situ growth of Bi2S3, cysteine also can be used as the sulfur source [27]. The shape of Bi2S3 obtained by using cysteine as the sulfur source is significantly different from that obtained by using thiourea, indicating that the sulfur source has a great impact on the formation of Bi2S3, which will also be our plan for further research.

Figure 8 FESEM images of (a) TiO2, (b) BiVO4/TiO2 (c) BVT (1.5 h), (d) BVT (3 h), (e) BVT (5 h）and (f) BVT (7 h).
Figure 8

FESEM images of (a) TiO2, (b) BiVO4/TiO2 (c) BVT (1.5 h), (d) BVT (3 h), (e) BVT (5 h）and (f) BVT (7 h).

We have tested and analyzed the cross-sectional morphology of the Bi2S3/BiVO4/TiO2 ternary heterojunction, as shown in Figure 9(a). TiO2 nanorods grown on FTO substrates and some BiVO4 and Bi2S3 nanomaterials can be clearly seen. The morphology of BiVO4 is consistent with the results observed in top view SEM. Bi2S3 exhibits a rod-like structure, which is consistent with the SEM results shown in Figure 8(f). A line scan test was conducted on the yellow line marked portion in Figure 9 to analyze the elemental composition of the substance. In Figure 9(b), it can be found that the distribution of Si, Sn, O, Na, and Mg elements is mainly in the substrate. These elements mainly come from glass and FTO films. The Ti element is mainly distributed in the middle of the online scanning, which corresponds to the hydrothermal generation of TiO2 nanorods. Bi, S, and V mainly focus on the top portion of the line scanning test, which correspond to BiVO4 and Bi2S3 nanomaterials. The cross-sectional SEM and line scanning test results of the Bi2S3/BiVO4/TiO2 ternary heterojunction are consistent with the XRD results.

Figure 9 (a) SEM image of Bi2S3/BiVO4/TiO2 cross section and (b) line scanning of selected areas in (a).
Figure 9

(a) SEM image of Bi2S3/BiVO4/TiO2 cross section and (b) line scanning of selected areas in (a).

To investigate the surface chemical compositions and the chemical states of each element, XPS measurement was recorded [28,29]. XPS testing was performed on both BiVO4/TiO2 and Bi2S3/BiVO4/TiO2 samples, as shown in Figure 10(a). The full spectrum shows five elements, Bi, O, Ti, V, and S for Bi2S3/BiVO4/TiO2. All elemental binding energies are calibrated with C 1s binding energy. Comparing the full spectra of BiVO4/TiO2 and Bi2S3/BiVO4/TiO2 samples, it can be found that there is a peak of S 2s at 225 eV in the spectral line of Bi2S3/BiVO4/TiO2 (Figure 10(b)). Figure 10(c)–(j) shows the high-resolution XPS spectra of all elements. Figure 10(c) and (d) show the XPS patterns of the Ti element. In Figure 10(c), the two peaks of Ti 2p are at 465.2 eV and 457.9 eV binding energies, corresponding to Ti 2p1/2 and Ti 2p3/2, respectively, indicating that Ti element appeared in the BiVO4/TiO2 composite. In Figure 10(d), the peak of Ti 2p3/2 is located at 458.5 eV. The energy differences between Ti 2p1/2 and Ti 2p3/2 are 7.3 eV (for BiVO4/TiO2) and 6.7 eV (for Bi2S3/BiVO4/TiO2). This indicates that the formation of Bi2S3 has a certain impact on the peak position of the Ti element. In Figure 10(e), the O1s peak splits into a main peak at 529.1 eV and a small shoulder at 530.7 eV, which are corresponding to the lattice oxygen and surface adsorbed oxygen, respectively. However, in Figure 10(f), it is found that the peak position of O1s simultaneously moves slightly toward the high energy portion. For the Bi 4f high-resolution XPS spectra, the two peaks of Bi 4f at 163.7 eV and 158.4 eV/158.5 eV binding energy, corresponding to Bi 4f5/2 and Bi 4f7/2, respectively, can be proved to be Bi3 + in Bi2S3. Comparing Figure 10(g) and (h), it is found that a weak peak appears in Figure 10(h). The peak of S2p at 161.0 eV binding energies corresponds to S 2p1/2, which indicates that the S element is S2− in Bi2S3. In Figure 10(i), the binding energy peaks at 523.3 and 515.9 eV correspond to V 2p1/2 and V 2p3/2 and are attributed to V5+ in BiVO4. In Figure 10(j), the binding energy peaks are located at 524.2 and 516.8 eV, respectively. In the sample Bi2S3/BiVO4/TiO2, the peak position of V also shifted slightly toward the high energy direction. From the XPS pattern analysis and combined with the XRD pattern, the sample contains TiO2, BiVO4, and Bi2S3, indicating that the Bi2S3/BiVO4/TiO2 ternary compliant photoanode material was successfully prepared, which is matched with the expected results.

Figure 10 XPS patterns of (a) survey spectrum of VT and BVT, (b)S-2s of BVT, (c) Ti-2p of VT, (d) Ti-2p of BVT, (e) O-1s of VT, (f) O-1s of BVT, (g) Bi-4f of VT, (h) Bi-4f and S-2p of BVT, (i) V-2p of VT, and (j) V-2p of BVT.
Figure 10 XPS patterns of (a) survey spectrum of VT and BVT, (b)S-2s of BVT, (c) Ti-2p of VT, (d) Ti-2p of BVT, (e) O-1s of VT, (f) O-1s of BVT, (g) Bi-4f of VT, (h) Bi-4f and S-2p of BVT, (i) V-2p of VT, and (j) V-2p of BVT.
Figure 10

XPS patterns of (a) survey spectrum of VT and BVT, (b)S-2s of BVT, (c) Ti-2p of VT, (d) Ti-2p of BVT, (e) O-1s of VT, (f) O-1s of BVT, (g) Bi-4f of VT, (h) Bi-4f and S-2p of BVT, (i) V-2p of VT, and (j) V-2p of BVT.

The absorption response properties of pure TiO2, binary photocatalyst VT, and ternary photocatalyst BVT (5 h) were carried out. In Figure 11(a), the TiO2 nanorod arrays respond almost exclusively to UV light at wavelengths less than 400 nm, and after modification with BiVO4, the light absorption edge expands to 600 nm, indicating a red shift, along with a certain increase in light absorption intensity. After in situ conversion to generate ternary composite photocatalysts, the light absorption intensity increases significantly, and the light absorption limit is further broadened. It is mainly due to the adhesion of BiVO4 and Bi2S3, which narrows the band gap of the composite. These results indicate that the co-modification of BiVO4 and Bi2S3 significantly improves light absorption intensity and extends the light absorption range. In conclusion, it can be guessed that the ternary composite photocatalyst has the strongest response to visible light absorption, which is significantly stronger than TiO2 nanorods and binary materials. According to the Tauc plot fit in Figure 11(b) and the band gap equation: ( α hv ) 2 = A ( hv − E g ) , so the band gaps of TiO2, binary heterojunction VT, and ternary heterojunction BVT (5 h) are 3.01, 2.36, and 1.98 eV, respectively, and the BVT (5 h) with narrowed band gap shows the strongest absorption of visible light.

Figure 11 (a) UV-Vis absorption spectra and (b) plots of (ahv)2 versus energy (hv) of TiO2, VT and BVT(5h).
Figure 11

(a) UV-Vis absorption spectra and (b) plots of (ahv)2 versus energy (hv) of TiO2, VT and BVT(5h).

To investigate the photogenerated carrier transport mechanism, electrochemical tests were performed. The photocurrent response of the sample in the electrolyte solution can directly reflect the photogenerated carrier production and transfer [24]. Figure 12 shows the transient photocurrent plots, electrochemical impedance plots, and Mott–Schottky plots of Bi2S3/BiVO4/TiO2 with different hydrothermal times. According to Figure 12(a), the Bi2S3/BiVO4/TiO2 composites prepared with different hydrothermal times are all very sensitive to light irradiation. When light is irradiated, the electrons inside the composite material are jumped by light excitation to produce photo-generated electron–hole, so there is a large instantaneous photocurrent, which corresponds to the sharp part in the curve, and with the increase of light time, a part of the broad-generated electron–hole pairs inside the material will be compounded, and the compounded carriers and separated carriers reach some kind of balance and tend to the steady state. When the light source is removed, the current decreases instantaneously. The photocurrent of the ternary heterojunction is significantly larger than TiO2 and BiVO4/TiO2 composites when illuminated, and the photocurrent density increases gradually with the increase of hydrothermal time, reaching a maximum value of 0.514 mA/cm2 at 5 h. However, the photocurrent density decreased when the hydrothermal time reached 7 h, probably due to the accumulation of too much Bi2S3, which increases the interfacial resistance, while a new composite may be formed centers [30], an increase in electron–hole pair complexation, and a decrease in the separation rate. The EIS profiles of different photo-anode materials are shown in Figure 12(b), and the curvature of the curves are basically presented, and the radius of curvature is TiO2 > VT > BVT (7 h) > BVT (1.5 h) > BVT (3 h) > BVT (5 h) in a descending order, and the smaller radius of curvature indicates that electrons encounter less obstruction in the transmission process, and the corresponding AC impedance is smaller. Therefore, BVT (5 h) has the smallest interfacial resistance and the smallest electron loss during charge transfer compared with other samples, which is more favorable for interfacial electron transfer and suppresses carrier complexion at the same time. The slopes of Mott–Schottky (M–S) curves of different samples are positive (Figure 12(c)), which can indicate that these samples are all n-type semiconductors. The flat-band potential E fb can be calculated based on the following formula:

1 C 2 = 2 e ϵ ε 0 N D ( E − E fb − k B e T ) ,

where C denotes the capacitance at the electrolyte interface, e and q are the charge (1.6 × 10−19 C), ε is relative permittivity, ε 0 is the vacuum permittivity (8.85 × 10−14 F cm−1), N D is the charge carrier concentration, E is the applied potential, E fb is the flat-band potential, k B is the Boltzmann constant (1.381 × 10−23 J K−1), and T is the temperature [31,32]. E fb was calculated from the intercept of the 1/C 2 curve versus the x-axis [33], and the calculation values are shown in Table 1. The flat-band potentials of different samples are BVT (7 h) > BVT (3 h) > BVT (1.5 h) > BVT (5 h) in a descending order, and the flat-band potential of the BVT (5 h) sample is negative, indicating that it has the highest carrier concentration and the lowest charge recombination rate with the best photo-generated electron transport performance. The stability of current in photoanode materials under illumination is an issue that requires attention. We conducted a light stability test on the sample (BVT (5 h)) with the best photocurrent. Figure 12(d) shows the relationship between photocurrent density and illumination time. It can be seen that with the prolongation of lighting time, the photocurrent presents a downward trend. After 600 s of light irradiation, the photocurrent basically reaches a stable value.

Figure 12 (a) Transient photocurrent diagram; (b) electrochemical impedance diagram; (c) Mott–Schottky diagram of BVT; and (d) the relationship between current density and irradiation time of BVT (5 h).
Figure 12

(a) Transient photocurrent diagram; (b) electrochemical impedance diagram; (c) Mott–Schottky diagram of BVT; and (d) the relationship between current density and irradiation time of BVT (5 h).

Table 1

Flat band potential E fb of samples with different hydrothermal times

Sample E fb/V
BVT (1.5 h) −0.494
BVT (3 h) 0.487
BVT (5 h) −0.736
BVT (7 h) 0.556

3.3 Photoelectric conversion mechanism

Whether the heterojunction can effectively separate carriers depends on its energy band position. The E CB edge of the semiconductor at the point of zero charge can be calculated by the empirical equations:

E VB = χ − E e + 0 . 5 E g ,

E CB = E VB − E g ,

where E VB is the valence band-edge potential, E CB is the conduction band-edge potential, X is the electronegativity of the semiconductor, expressed as the geometric mean of the absolute electronegativity of the constituent atoms, E e is the energy of free electrons on the hydrogen scale (about 4.5 eV), and E g is the band gap of the semiconductor. Taking the absolute electronegativity values for Bi, V, S, Ti, and O as 4.69, 3.6, 6.22, 3.45, and 7.54, respectively, the X can be obtained, which are 5.56 eV (Bi2S3), 6.16 eV (BiVO4), and 5.81 eV (TiO2). On the basis of the aforementioned equations, we can obtain E CB and E VB values of different semiconductors (Table 2).

Based on the calculated values, E CB and E VB positions of BiVO4 are about 0.46 and 2.86 eV (relative to normal hydrogen electrode). Generally speaking, we deem BiVO4 as an intrinsic semiconductor, and its Fermi level (E F) would be in the middle of E CB and E VB. So, the BiVO4’s E F position is approximately around 1.6 eV [18,34,35]. In addition, the TiO2’s E F position is about −0.1 eV. When TiO2 and BiVO4 contact to form a heterojunction, their Fermi levels reach a unified state. After thermodynamical equilibrium, BiVO4’s E F reached to be the same as that of TiO2’s E F (−0.1 eV). So the E CB and E VB of BiVO4 will shift more negative potential. The E CB position of BiVO4 will change from 0.46 to −1.24 eV, and the E VB position will change from 2.86 to 1.16 eV. After thermodynamic equilibrium, photogenerated electrons are transferred from BiVO4 to TiO2 E CB due to energy band difference. Figure 13 displays the energy band diagram of TiO2 and BiVO4 before and after the heterojunction formation. After the formation of heterojunction between TiO2 and BiVO4, due to the difference in energy band, the electrons in the E CB of BiVO4 will transfer to the E CB of TiO2 to realize the separation of photogenerated carriers.

Figure 13 The diagram of the energy band before and after TiO2 and BiVO4 formation heterojunction.
Figure 13

The diagram of the energy band before and after TiO2 and BiVO4 formation heterojunction.

Under the simulated sunlight, both Bi2S3 and BiVO4 will produce free electrons and holes. Based on the traditional II-type heterojunction mechanism, the photo-generated electrons in Bi2S3 transfer from its E CB to the BiVO4’s E CB. The E CB position of Bi2S3 is higher than that of BiVO4. Likewise, generated holes in BiVO4 will transfer to E VB of Bi2S3 due to its E VB d position, which is more positive than that of Bi2S3. Eventually, the photo-generated electron–hole pairs are completely separated. It is also reported that Z-type heterojunction may also be formed between Bi2S3 and BiVO4 [36]. When Bi2S3 and BiVO4 absorbing the sunlight, there are numbers of free electrons and holes in the E CB and E VB, respectively. At this time, the electrons in the E CB of BiVO4 will transmigrate to the E VB of Bi2S3, accelerating the separation of electrons and holes in BiVO4 and Bi2S3. Z-scheme hetero-junction of BiVO4/Bi2S3 allows the electron transferring from BiVO4 to Bi2S3 and accumulated the electron and hole in BiVO4 and Bi2S3, respectively.

Table 2

Absolute electronegativity, energy band gap, calculated conduction, and valence band

Semiconductors X (eV) E g (eV) E cb (eV) E vb (eV)
TiO2 5.81 3.2 −0.29 2.91
BiVO4 6.16 2.4 0.46 2.86
Bi2S3 5.56 1.3 0.41 1.71

In the aforementioned discussion, the possible carrier transmission paths between BiVO4/TiO2 and BiVO4/Bi2S3 were analyzed. Bi2S3 was in situ grown on BiVO4 by the hydrothermal method. The ternary heterojunction Bi2S3/BiVO4/TiO2 was formed between TiO2, BiVO4, and TiO2. According to the electrochemical test, the Bi2S3/BiVO4/TiO2 heterojunction showed excellent photoelectric response, which is mainly due to the rapid separation between electrons and holes in the heterojunction. Figure 14 shows the two possible transmission processes of the electrons and holes in Bi2S3/BiVO4/TiO2 heterojunction, one is the traditional II-type heterojunction carrier transmission and the other is Z-scheme carrier transmission. In the conventional II-type heterojunction, it produces photo-generated carriers and transfers rapidly. The electron–hole pairs will be produced under the sun irradiation. The electrons in the E CB of Bi2S3 will transfer to the E CB of BiVO4 and TiO2. At the same time, the holes in the E VB of BiVO4 and TiO2 will shift to the E CB of Bi2S3, finally achieving the rapid separation of electron–hole pairs. There is another possible carrier transmission mode. Double Z-type heterojunction was formed in Bi2S3/BiVO4/TiO2 composite. When the visible light illuminate the Bi2S3/BiVO4/TiO2 composite, the electron–hole pairs will be generated in each part. The electrons in the E CB of TiO2 and BiVO4 will directly jump into the E VB of Bi2S3, which will lead to the accumulation of electrons in the E CB of Bi2S3 and also lead to the accumulation of the holes in the E VB of BiVO4 and TiO2. It is beneficial to improving the photocurrent response of the Bi2S3/BiVO4/TiO2 hetero-junction. Compared with the traditional II-type heterojunction, this double-Z heterojunction has higher transmission and separation efficiency of photo-generated carriers, which is more conducive to improving the photoelectric performance of the device.

Figure 14 The charge transfer mechanism for Bi2S3/BiVO4/TiO2.
Figure 14

The charge transfer mechanism for Bi2S3/BiVO4/TiO2.

4 Conclusions

In our work, the Bi2S3/BiVO4/TiO2 composites were created utilizing a simple hydrothermal method. Bi2S3/BiVO4/TiO2 composite has stronger visible light absorption capacity than that of pure TiO2 and BiVO4/TiO2, mainly due to the formation of ternary heterojunction. With the increase of the concentration of BiVO4 precursor solution, the morphology of BiVO4 changes from peanut to olive. Photo-electrochemical performance tests confirmed that BiVO4/TiO2 has better electron–hole pair separation and transport efficiency. Using thiourea as the sulfur source, BiVO4 is partially transformed into Bi2S3 on the BiVO4/TiO2 heterojunction and finally forms the Bi2S3/BiVO4/TiO2 heterojunction. The results showed that the Bi2S3/BiVO4/TiO2 has much higher photoelectric performance than pure TiO2 and BiVO4/TiO2. This extraordinary improvement in photoelectric performance is mainly due to the formation of heterojunction and the reduction of TiO2 optical band gap due to BiVO4 and Bi2S3. The simple method presented in this work could be used to fabricate composite heterojunction with excellent photoelectric performance in different fields, such as photo-anode, photo-catalyst, and photodetector.

  1. Funding information: This work was supported by National Natural Science Foundation of China (52272136) Henan Province high-end foreign introduction project (HNGD2023010), Natural Science Foundation of Jiangsu Province (BK20221402), and China Postdoctoral Science Foundation (2018M632771).

  2. Author contributions: All authors have accepted responsibility for the entire content of this manuscript and approved its submission.

  3. Conflict of interest: The authors state no conflict of interest.

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Received: 2023-02-09
Revised: 2023-04-03
Accepted: 2023-04-14
Published Online: 2023-05-24

© 2023 the author(s), published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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  56. High-performance lithium–selenium batteries enabled by nitrogen-doped porous carbon from peanut meal
  57. Investigating effects of Lorentz forces and convective heating on ternary hybrid nanofluid flow over a curved surface using homotopy analysis method
  58. Exploring the potential of biogenic magnesium oxide nanoparticles for cytotoxicity: In vitro and in silico studies on HCT116 and HT29 cells and DPPH radical scavenging
  59. Enhanced visible-light-driven photocatalytic degradation of azo dyes by heteroatom-doped nickel tungstate nanoparticles
  60. A facile method to synthesize nZVI-doped polypyrrole-based carbon nanotube for Ag(i) removal
  61. Improved osseointegration of dental titanium implants by TiO2 nanotube arrays with self-assembled recombinant IGF-1 in type 2 diabetes mellitus rat model
  62. Functionalized SWCNTs@Ag–TiO2 nanocomposites induce ROS-mediated apoptosis and autophagy in liver cancer cells
  63. Triboelectric nanogenerator based on a water droplet spring with a concave spherical surface for harvesting wave energy and detecting pressure
  64. A mathematical approach for modeling the blood flow containing nanoparticles by employing the Buongiorno’s model
  65. Molecular dynamics study on dynamic interlayer friction of graphene and its strain effect
  66. Induction of apoptosis and autophagy via regulation of AKT and JNK mitogen-activated protein kinase pathways in breast cancer cell lines exposed to gold nanoparticles loaded with TNF-α and combined with doxorubicin
  67. Effect of PVA fibers on durability of nano-SiO2-reinforced cement-based composites subjected to wet-thermal and chloride salt-coupled environment
  68. Effect of polyvinyl alcohol fibers on mechanical properties of nano-SiO2-reinforced geopolymer composites under a complex environment
  69. In vitro studies of titanium dioxide nanoparticles modified with glutathione as a potential drug delivery system
  70. Comparative investigations of Ag/H2O nanofluid and Ag-CuO/H2O hybrid nanofluid with Darcy-Forchheimer flow over a curved surface
  71. Study on deformation characteristics of multi-pass continuous drawing of micro copper wire based on crystal plasticity finite element method
  72. Properties of ultra-high-performance self-compacting fiber-reinforced concrete modified with nanomaterials
  73. Prediction of lap shear strength of GNP and TiO2/epoxy nanocomposite adhesives
  74. A novel exploration of how localized magnetic field affects vortex generation of trihybrid nanofluids
  75. Fabrication and physicochemical characterization of copper oxide–pyrrhotite nanocomposites for the cytotoxic effects on HepG2 cells and the mechanism
  76. Thermal radiative flow of cross nanofluid due to a stretched cylinder containing microorganisms
  77. In vitro study of the biphasic calcium phosphate/chitosan hybrid biomaterial scaffold fabricated via solvent casting and evaporation technique for bone regeneration
  78. Insights into the thermal characteristics and dynamics of stagnant blood conveying titanium oxide, alumina, and silver nanoparticles subject to Lorentz force and internal heating over a curved surface
  79. Effects of nano-SiO2 additives on carbon fiber-reinforced fly ash–slag geopolymer composites performance: Workability, mechanical properties, and microstructure
  80. Energy bandgap and thermal characteristics of non-Darcian MHD rotating hybridity nanofluid thin film flow: Nanotechnology application
  81. Green synthesis and characterization of ginger-extract-based oxali-palladium nanoparticles for colorectal cancer: Downregulation of REG4 and apoptosis induction
  82. Abnormal evolution of resistivity and microstructure of annealed Ag nanoparticles/Ag–Mo films
  83. Preparation of water-based dextran-coated Fe3O4 magnetic fluid for magnetic hyperthermia
  84. Statistical investigations and morphological aspects of cross-rheological material suspended in transportation of alumina, silica, titanium, and ethylene glycol via the Galerkin algorithm
  85. Effect of CNT film interleaves on the flexural properties and strength after impact of CFRP composites
  86. Self-assembled nanoscale entities: Preparative process optimization, payload release, and enhanced bioavailability of thymoquinone natural product
  87. Structure–mechanical property relationships of 3D-printed porous polydimethylsiloxane films
  88. Nonlinear thermal radiation and the slip effect on a 3D bioconvection flow of the Casson nanofluid in a rotating frame via a homotopy analysis mechanism
  89. Residual mechanical properties of concrete incorporated with nano supplementary cementitious materials exposed to elevated temperature
  90. Time-independent three-dimensional flow of a water-based hybrid nanofluid past a Riga plate with slips and convective conditions: A homotopic solution
  91. Lightweight and high-strength polyarylene ether nitrile-based composites for efficient electromagnetic interference shielding
  92. Review Articles
  93. Recycling waste sources into nanocomposites of graphene materials: Overview from an energy-focused perspective
  94. Hybrid nanofiller reinforcement in thermoset and biothermoset applications: A review
  95. Current state-of-the-art review of nanotechnology-based therapeutics for viral pandemics: Special attention to COVID-19
  96. Solid lipid nanoparticles for targeted natural and synthetic drugs delivery in high-incidence cancers, and other diseases: Roles of preparation methods, lipid composition, transitional stability, and release profiles in nanocarriers’ development
  97. Critical review on experimental and theoretical studies of elastic properties of wurtzite-structured ZnO nanowires
  98. Polyurea micro-/nano-capsule applications in construction industry: A review
  99. A comprehensive review and clinical guide to molecular and serological diagnostic tests and future development: In vitro diagnostic testing for COVID-19
  100. Recent advances in electrocatalytic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid: Mechanism, catalyst, coupling system
  101. Research progress and prospect of silica-based polymer nanofluids in enhanced oil recovery
  102. Review of the pharmacokinetics of nanodrugs
  103. Engineered nanoflowers, nanotrees, nanostars, nanodendrites, and nanoleaves for biomedical applications
  104. Research progress of biopolymers combined with stem cells in the repair of intrauterine adhesions
  105. Progress in FEM modeling on mechanical and electromechanical properties of carbon nanotube cement-based composites
  106. Antifouling induced by surface wettability of poly(dimethyl siloxane) and its nanocomposites
  107. TiO2 aerogel composite high-efficiency photocatalysts for environmental treatment and hydrogen energy production
  108. Structural properties of alumina surfaces and their roles in the synthesis of environmentally persistent free radicals (EPFRs)
  109. Nanoparticles for the potential treatment of Alzheimer’s disease: A physiopathological approach
  110. Current status of synthesis and consolidation strategies for thermo-resistant nanoalloys and their general applications
  111. Recent research progress on the stimuli-responsive smart membrane: A review
  112. Dispersion of carbon nanotubes in aqueous cementitious materials: A review
  113. Applications of DNA tetrahedron nanostructure in cancer diagnosis and anticancer drugs delivery
  114. Magnetic nanoparticles in 3D-printed scaffolds for biomedical applications
  115. An overview of the synthesis of silicon carbide–boron carbide composite powders
  116. Organolead halide perovskites: Synthetic routes, structural features, and their potential in the development of photovoltaic
  117. Recent advancements in nanotechnology application on wood and bamboo materials: A review
  118. Application of aptamer-functionalized nanomaterials in molecular imaging of tumors
  119. Recent progress on corrosion mechanisms of graphene-reinforced metal matrix composites
  120. Research progress on preparation, modification, and application of phenolic aerogel
  121. Application of nanomaterials in early diagnosis of cancer
  122. Plant mediated-green synthesis of zinc oxide nanoparticles: An insight into biomedical applications
  123. Recent developments in terahertz quantum cascade lasers for practical applications
  124. Recent progress in dielectric/metal/dielectric electrodes for foldable light-emitting devices
  125. Nanocoatings for ballistic applications: A review
  126. A mini-review on MoS2 membrane for water desalination: Recent development and challenges
  127. Recent updates in nanotechnological advances for wound healing: A narrative review
  128. Recent advances in DNA nanomaterials for cancer diagnosis and treatment
  129. Electrochemical micro- and nanobiosensors for in vivo reactive oxygen/nitrogen species measurement in the brain
  130. Advances in organic–inorganic nanocomposites for cancer imaging and therapy
  131. Advancements in aluminum matrix composites reinforced with carbides and graphene: A comprehensive review
  132. Modification effects of nanosilica on asphalt binders: A review
  133. Decellularized extracellular matrix as a promising biomaterial for musculoskeletal tissue regeneration
  134. Review of the sol–gel method in preparing nano TiO2 for advanced oxidation process
  135. Micro/nano manufacturing aircraft surface with anti-icing and deicing performances: An overview
  136. Cell type-targeting nanoparticles in treating central nervous system diseases: Challenges and hopes
  137. An overview of hydrogen production from Al-based materials
  138. A review of application, modification, and prospect of melamine foam
  139. A review of the performance of fibre-reinforced composite laminates with carbon nanotubes
  140. Research on AFM tip-related nanofabrication of two-dimensional materials
  141. Advances in phase change building materials: An overview
  142. Development of graphene and graphene quantum dots toward biomedical engineering applications: A review
  143. Nanoremediation approaches for the mitigation of heavy metal contamination in vegetables: An overview
  144. Photodynamic therapy empowered by nanotechnology for oral and dental science: Progress and perspectives
  145. Biosynthesis of metal nanoparticles: Bioreduction and biomineralization
  146. Current diagnostic and therapeutic approaches for severe acute respiratory syndrome coronavirus-2 (SARS-COV-2) and the role of nanomaterial-based theragnosis in combating the pandemic
  147. Application of two-dimensional black phosphorus material in wound healing
  148. Special Issue on Advanced Nanomaterials and Composites for Energy Conversion and Storage - Part I
  149. Helical fluorinated carbon nanotubes/iron(iii) fluoride hybrid with multilevel transportation channels and rich active sites for lithium/fluorinated carbon primary battery
  150. The progress of cathode materials in aqueous zinc-ion batteries
  151. Special Issue on Advanced Nanomaterials for Carbon Capture, Environment and Utilization for Energy Sustainability - Part I
  152. Effect of polypropylene fiber and nano-silica on the compressive strength and frost resistance of recycled brick aggregate concrete
  153. Mechanochemical design of nanomaterials for catalytic applications with a benign-by-design focus
https://doi.org/10.1515/ntrev-2022-0550
Keywords for this article
TiO2/BiVO4/Bi2S3 heterojunction; composite materials; photoelectric performance
Creative Commons
BY 4.0

Articles in the same Issue

  1. Research Articles
  2. Preparation of CdS–Ag2S nanocomposites by ultrasound-assisted UV photolysis treatment and its visible light photocatalysis activity
  3. Significance of nanoparticle radius and inter-particle spacing toward the radiative water-based alumina nanofluid flow over a rotating disk
  4. Aptamer-based detection of serotonin based on the rapid in situ synthesis of colorimetric gold nanoparticles
  5. Investigation of the nucleation and growth behavior of Ti2AlC and Ti3AlC nano-precipitates in TiAl alloys
  6. Dynamic recrystallization behavior and nucleation mechanism of dual-scale SiCp/A356 composites processed by P/M method
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  9. Study on the chronic toxicity and carcinogenicity of iron-based bioabsorbable stents
  10. Influence of microalloying with B on the microstructure and properties of brazed joints with Ag–Cu–Zn–Sn filler metal
  11. Thermohydraulic performance of thermal system integrated with twisted turbulator inserts using ternary hybrid nanofluids
  12. Study of mechanical properties of epoxy/graphene and epoxy/halloysite nanocomposites
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  14. Cu and Al2O3-based hybrid nanofluid flow through a porous cavity
  15. Design of functional vancomycin-embedded bio-derived extracellular matrix hydrogels for repairing infectious bone defects
  16. Study on nanocrystalline coating prepared by electro-spraying 316L metal wire and its corrosion performance
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  18. Tungsten trioxide nanocomposite for conventional soliton and noise-like pulse generation in anomalous dispersion laser cavity
  19. Microstructure and electrical contact behavior of the nano-yttria-modified Cu-Al2O3/30Mo/3SiC composite
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  23. Chitosan-capped silver nanoparticles with potent and selective intrinsic activity against the breast cancer cells
  24. Multi-core/shell SiO2@Al2O3 nanostructures deposited on Ti3AlC2 to enhance high-temperature stability and microwave absorption properties
  25. Solution-processed Bi2S3/BiVO4/TiO2 ternary heterojunction photoanode with enhanced photoelectrochemical performance
  26. Electroporation effect of ZnO nanoarrays under low voltage for water disinfection
  27. NIR-II window absorbing graphene oxide-coated gold nanorods and graphene quantum dot-coupled gold nanorods for photothermal cancer therapy
  28. Nonlinear three-dimensional stability characteristics of geometrically imperfect nanoshells under axial compression and surface residual stress
  29. Investigation of different nanoparticles properties on the thermal conductivity and viscosity of nanofluids by molecular dynamics simulation
  30. Optimized Cu2O-{100} facet for generation of different reactive oxidative species via peroxymonosulfate activation at specific pH values to efficient acetaminophen removal
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  33. Synthesis of Ag and Cu nanoparticles by plasma discharge in inorganic salt solutions
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  36. Mechanical performance of date palm fiber-reinforced concrete modified with nano-activated carbon
  37. Melting point of dried gold nanoparticles prepared with ultrasonic spray pyrolysis and lyophilisation
  38. Graphene nanofibers: A modern approach towards tailored gypsum composites
  39. Role of localized magnetic field in vortex generation in tri-hybrid nanofluid flow: A numerical approach
  40. Intelligent computing for the double-diffusive peristaltic rheology of magneto couple stress nanomaterials
  41. Bioconvection transport of upper convected Maxwell nanoliquid with gyrotactic microorganism, nonlinear thermal radiation, and chemical reaction
  42. 3D printing of porous Ti6Al4V bone tissue engineering scaffold and surface anodization preparation of nanotubes to enhance its biological property
  43. Bioinspired ferromagnetic CoFe2O4 nanoparticles: Potential pharmaceutical and medical applications
  44. Significance of gyrotactic microorganisms on the MHD tangent hyperbolic nanofluid flow across an elastic slender surface: Numerical analysis
  45. Performance of polycarboxylate superplasticisers in seawater-blended cement: Effect from chemical structure and nano modification
  46. Entropy minimization of GO–Ag/KO cross-hybrid nanofluid over a convectively heated surface
  47. Oxygen plasma assisted room temperature bonding for manufacturing SU-8 polymer micro/nanoscale nozzle
  48. Performance and mechanism of CO2 reduction by DBD-coupled mesoporous SiO2
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  50. Exploration of generalized two-phase free convection magnetohydrodynamic flow of dusty tetra-hybrid Casson nanofluid between parallel microplates
  51. Hygrothermal bending analysis of sandwich nanoplates with FG porous core and piezomagnetic faces via nonlocal strain gradient theory
  52. Design and optimization of a TiO2/RGO-supported epoxy multilayer microwave absorber by the modified local best particle swarm optimization algorithm
  53. Mechanical properties and frost resistance of recycled brick aggregate concrete modified by nano-SiO2
  54. Self-template synthesis of hollow flower-like NiCo2O4 nanoparticles as an efficient bifunctional catalyst for oxygen reduction and oxygen evolution in alkaline media
  55. High-performance wearable flexible strain sensors based on an AgNWs/rGO/TPU electrospun nanofiber film for monitoring human activities
  56. High-performance lithium–selenium batteries enabled by nitrogen-doped porous carbon from peanut meal
  57. Investigating effects of Lorentz forces and convective heating on ternary hybrid nanofluid flow over a curved surface using homotopy analysis method
  58. Exploring the potential of biogenic magnesium oxide nanoparticles for cytotoxicity: In vitro and in silico studies on HCT116 and HT29 cells and DPPH radical scavenging
  59. Enhanced visible-light-driven photocatalytic degradation of azo dyes by heteroatom-doped nickel tungstate nanoparticles
  60. A facile method to synthesize nZVI-doped polypyrrole-based carbon nanotube for Ag(i) removal
  61. Improved osseointegration of dental titanium implants by TiO2 nanotube arrays with self-assembled recombinant IGF-1 in type 2 diabetes mellitus rat model
  62. Functionalized SWCNTs@Ag–TiO2 nanocomposites induce ROS-mediated apoptosis and autophagy in liver cancer cells
  63. Triboelectric nanogenerator based on a water droplet spring with a concave spherical surface for harvesting wave energy and detecting pressure
  64. A mathematical approach for modeling the blood flow containing nanoparticles by employing the Buongiorno’s model
  65. Molecular dynamics study on dynamic interlayer friction of graphene and its strain effect
  66. Induction of apoptosis and autophagy via regulation of AKT and JNK mitogen-activated protein kinase pathways in breast cancer cell lines exposed to gold nanoparticles loaded with TNF-α and combined with doxorubicin
  67. Effect of PVA fibers on durability of nano-SiO2-reinforced cement-based composites subjected to wet-thermal and chloride salt-coupled environment
  68. Effect of polyvinyl alcohol fibers on mechanical properties of nano-SiO2-reinforced geopolymer composites under a complex environment
  69. In vitro studies of titanium dioxide nanoparticles modified with glutathione as a potential drug delivery system
  70. Comparative investigations of Ag/H2O nanofluid and Ag-CuO/H2O hybrid nanofluid with Darcy-Forchheimer flow over a curved surface
  71. Study on deformation characteristics of multi-pass continuous drawing of micro copper wire based on crystal plasticity finite element method
  72. Properties of ultra-high-performance self-compacting fiber-reinforced concrete modified with nanomaterials
  73. Prediction of lap shear strength of GNP and TiO2/epoxy nanocomposite adhesives
  74. A novel exploration of how localized magnetic field affects vortex generation of trihybrid nanofluids
  75. Fabrication and physicochemical characterization of copper oxide–pyrrhotite nanocomposites for the cytotoxic effects on HepG2 cells and the mechanism
  76. Thermal radiative flow of cross nanofluid due to a stretched cylinder containing microorganisms
  77. In vitro study of the biphasic calcium phosphate/chitosan hybrid biomaterial scaffold fabricated via solvent casting and evaporation technique for bone regeneration
  78. Insights into the thermal characteristics and dynamics of stagnant blood conveying titanium oxide, alumina, and silver nanoparticles subject to Lorentz force and internal heating over a curved surface
  79. Effects of nano-SiO2 additives on carbon fiber-reinforced fly ash–slag geopolymer composites performance: Workability, mechanical properties, and microstructure
  80. Energy bandgap and thermal characteristics of non-Darcian MHD rotating hybridity nanofluid thin film flow: Nanotechnology application
  81. Green synthesis and characterization of ginger-extract-based oxali-palladium nanoparticles for colorectal cancer: Downregulation of REG4 and apoptosis induction
  82. Abnormal evolution of resistivity and microstructure of annealed Ag nanoparticles/Ag–Mo films
  83. Preparation of water-based dextran-coated Fe3O4 magnetic fluid for magnetic hyperthermia
  84. Statistical investigations and morphological aspects of cross-rheological material suspended in transportation of alumina, silica, titanium, and ethylene glycol via the Galerkin algorithm
  85. Effect of CNT film interleaves on the flexural properties and strength after impact of CFRP composites
  86. Self-assembled nanoscale entities: Preparative process optimization, payload release, and enhanced bioavailability of thymoquinone natural product
  87. Structure–mechanical property relationships of 3D-printed porous polydimethylsiloxane films
  88. Nonlinear thermal radiation and the slip effect on a 3D bioconvection flow of the Casson nanofluid in a rotating frame via a homotopy analysis mechanism
  89. Residual mechanical properties of concrete incorporated with nano supplementary cementitious materials exposed to elevated temperature
  90. Time-independent three-dimensional flow of a water-based hybrid nanofluid past a Riga plate with slips and convective conditions: A homotopic solution
  91. Lightweight and high-strength polyarylene ether nitrile-based composites for efficient electromagnetic interference shielding
  92. Review Articles
  93. Recycling waste sources into nanocomposites of graphene materials: Overview from an energy-focused perspective
  94. Hybrid nanofiller reinforcement in thermoset and biothermoset applications: A review
  95. Current state-of-the-art review of nanotechnology-based therapeutics for viral pandemics: Special attention to COVID-19
  96. Solid lipid nanoparticles for targeted natural and synthetic drugs delivery in high-incidence cancers, and other diseases: Roles of preparation methods, lipid composition, transitional stability, and release profiles in nanocarriers’ development
  97. Critical review on experimental and theoretical studies of elastic properties of wurtzite-structured ZnO nanowires
  98. Polyurea micro-/nano-capsule applications in construction industry: A review
  99. A comprehensive review and clinical guide to molecular and serological diagnostic tests and future development: In vitro diagnostic testing for COVID-19
  100. Recent advances in electrocatalytic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid: Mechanism, catalyst, coupling system
  101. Research progress and prospect of silica-based polymer nanofluids in enhanced oil recovery
  102. Review of the pharmacokinetics of nanodrugs
  103. Engineered nanoflowers, nanotrees, nanostars, nanodendrites, and nanoleaves for biomedical applications
  104. Research progress of biopolymers combined with stem cells in the repair of intrauterine adhesions
  105. Progress in FEM modeling on mechanical and electromechanical properties of carbon nanotube cement-based composites
  106. Antifouling induced by surface wettability of poly(dimethyl siloxane) and its nanocomposites
  107. TiO2 aerogel composite high-efficiency photocatalysts for environmental treatment and hydrogen energy production
  108. Structural properties of alumina surfaces and their roles in the synthesis of environmentally persistent free radicals (EPFRs)
  109. Nanoparticles for the potential treatment of Alzheimer’s disease: A physiopathological approach
  110. Current status of synthesis and consolidation strategies for thermo-resistant nanoalloys and their general applications
  111. Recent research progress on the stimuli-responsive smart membrane: A review
  112. Dispersion of carbon nanotubes in aqueous cementitious materials: A review
  113. Applications of DNA tetrahedron nanostructure in cancer diagnosis and anticancer drugs delivery
  114. Magnetic nanoparticles in 3D-printed scaffolds for biomedical applications
  115. An overview of the synthesis of silicon carbide–boron carbide composite powders
  116. Organolead halide perovskites: Synthetic routes, structural features, and their potential in the development of photovoltaic
  117. Recent advancements in nanotechnology application on wood and bamboo materials: A review
  118. Application of aptamer-functionalized nanomaterials in molecular imaging of tumors
  119. Recent progress on corrosion mechanisms of graphene-reinforced metal matrix composites
  120. Research progress on preparation, modification, and application of phenolic aerogel
  121. Application of nanomaterials in early diagnosis of cancer
  122. Plant mediated-green synthesis of zinc oxide nanoparticles: An insight into biomedical applications
  123. Recent developments in terahertz quantum cascade lasers for practical applications
  124. Recent progress in dielectric/metal/dielectric electrodes for foldable light-emitting devices
  125. Nanocoatings for ballistic applications: A review
  126. A mini-review on MoS2 membrane for water desalination: Recent development and challenges
  127. Recent updates in nanotechnological advances for wound healing: A narrative review
  128. Recent advances in DNA nanomaterials for cancer diagnosis and treatment
  129. Electrochemical micro- and nanobiosensors for in vivo reactive oxygen/nitrogen species measurement in the brain
  130. Advances in organic–inorganic nanocomposites for cancer imaging and therapy
  131. Advancements in aluminum matrix composites reinforced with carbides and graphene: A comprehensive review
  132. Modification effects of nanosilica on asphalt binders: A review
  133. Decellularized extracellular matrix as a promising biomaterial for musculoskeletal tissue regeneration
  134. Review of the sol–gel method in preparing nano TiO2 for advanced oxidation process
  135. Micro/nano manufacturing aircraft surface with anti-icing and deicing performances: An overview
  136. Cell type-targeting nanoparticles in treating central nervous system diseases: Challenges and hopes
  137. An overview of hydrogen production from Al-based materials
  138. A review of application, modification, and prospect of melamine foam
  139. A review of the performance of fibre-reinforced composite laminates with carbon nanotubes
  140. Research on AFM tip-related nanofabrication of two-dimensional materials
  141. Advances in phase change building materials: An overview
  142. Development of graphene and graphene quantum dots toward biomedical engineering applications: A review
  143. Nanoremediation approaches for the mitigation of heavy metal contamination in vegetables: An overview
  144. Photodynamic therapy empowered by nanotechnology for oral and dental science: Progress and perspectives
  145. Biosynthesis of metal nanoparticles: Bioreduction and biomineralization
  146. Current diagnostic and therapeutic approaches for severe acute respiratory syndrome coronavirus-2 (SARS-COV-2) and the role of nanomaterial-based theragnosis in combating the pandemic
  147. Application of two-dimensional black phosphorus material in wound healing
  148. Special Issue on Advanced Nanomaterials and Composites for Energy Conversion and Storage - Part I
  149. Helical fluorinated carbon nanotubes/iron(iii) fluoride hybrid with multilevel transportation channels and rich active sites for lithium/fluorinated carbon primary battery
  150. The progress of cathode materials in aqueous zinc-ion batteries
  151. Special Issue on Advanced Nanomaterials for Carbon Capture, Environment and Utilization for Energy Sustainability - Part I
  152. Effect of polypropylene fiber and nano-silica on the compressive strength and frost resistance of recycled brick aggregate concrete
  153. Mechanochemical design of nanomaterials for catalytic applications with a benign-by-design focus
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