Next Article in Journal
Architectural and Urban Changes in a Residential Environment—Implications for Design Science
Previous Article in Journal
The Impacts of the Poverty Alleviation Relocation Program (PARP) on Households’ Education Investment: Evidence from a Quasi-Experiment in Rural China
 
 
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Facile Fabrication of SrTiO3/In2O3 on Carbon Fibers via a Self-Assembly Strategy for Enhanced Photocatalytic Hydrogen Production

1
School of Textile and Clothing and Arts and Media, Suzhou Institute of Trade & Commerce, Suzhou 215009, China
2
College of Textile Science and Engineering, Zhejiang Sci-Tech University, Hangzhou 310018, China
3
School of Social Development and Public Administration, Suzhou University of Science and Technology, Suzhou 215009, China
4
National Engineering Laboratory for Modern Silk, College of Textile and Clothing Engineering, Soochow University, Suzhou 215123, China
*
Author to whom correspondence should be addressed.
Sustainability 2024, 16(10), 3988; https://doi.org/10.3390/su16103988
Submission received: 30 January 2024 / Revised: 29 April 2024 / Accepted: 30 April 2024 / Published: 10 May 2024

Abstract

:
Photocatalytic water splitting by semiconductors is considered a promising and cost-effective method for achieving sustainable hydrogen production. In this study, a CF/SrTiO3/In2O3 photocatalytic material with a double-layer core–shell structure was developed. The experimental results indicated that the produced CF/SrTiO3/In2O3 composite fiber displayed superior photocatalytic hydrogen production performance, achieving a hydrogen evolution rate of approximately 320.71 μmol/g·h, which is roughly seven times higher than that of the CF/SrTiO3 fiber alone. The enhanced photocatalytic activity of the CF/SrTiO3/In2O3 fiber can be attributed to the heterojunction structure enriched with oxygen vacancies. It was found that these oxygen vacancies created defective states that served as traps for photogenerated electrons, facilitating their migration to the surface defect states and enabling the reduction of H+ in water to produce hydrogen. Furthermore, the synergy between the heterojunction structure and the conductivity of the carbon fiber promoted the generation and migration of photogenerated electrons, reduced the recombination of photogenerated electron–hole pairs, and ultimately improved photocatalytic hydrogen production. This study presents a new approach for designing efficient photocatalysts with surface oxygen vacancies on carbon fibers, providing new insights into the sustainable application of photocatalysts.

1. Introduction

It is widely acknowledged that the ongoing consumption of non-renewable resources, such as coal, petroleum, and natural gas, is leading us toward a significant global energy shortage. In response to this foreseeable crisis, scientists around the world are actively exploring renewable energy sources as alternatives. Out of the many options available, hydrogen energy has emerged as a highly promising option. It offers significant advantages, including a high heating value, extensive availability, and the absence of secondary pollutants from its combustion. Additionally, hydrogen energy has the potential for efficient transportation and storage.
Since Fujishima and Honda first reported on photocatalytic water splitting in 1972, semiconductor photocatalytic water splitting has been identified as a viable and cost-effective method for achieving sustainable hydrogen supply [1,2,3]. SrTiO3, with its perovskite structure, is a material of interest for photocatalytic hydrogen evolution because of its excellent energy band position and great chemical stability. Nevertheless, the photocatalytic performance of pure SrTiO3 is easily limited by the rapid recombination of photoinduced carriers, resulting in low photocatalytic efficiency and consequently impeding its practical application. In2O3, a significant N-type semiconductor, exhibits a band gap of approximately 2.8 eV and typically exists in a stable cubic crystal form with low resistivity and exceptional surface properties. It is an ideal material for photocatalytic applications and has seen widespread use in both photocatalytic sewage treatment and hydrogen evolution through photocatalytic water splitting [4]. A multitude of studies have been conducted on the development of photocatalytic composite materials that incorporate In2O3. For example, Satyabadi et al. [5] modified ZnO with In2O3, and their experiments confirmed that this modification significantly enhanced the absorption ability of ZnO in the visible region, greatly reduced the particle size of ZnO, and delayed the recombination of carriers. In their study, all In2O3-modified ZnO samples exhibited high photocatalytic hydrogen evolution activity under visible light. Similarly, Liu et al. [6] successfully synthesized a hierarchical porous hydrangea-like In2S3/In2O3 heterojunction structure using a simple in situ oxidation technique. Comparative studies demonstrated that this heterojunction structure substantially promoted photocatalytic hydrogen evolution compared to pure In2S3 and In2O3. However, research on enhancing the photocatalytic hydrogen evolution performance of SrTiO3 by modifying it with In2O3 remains limited [7,8,9].
Carbon fiber (CF) is highly valued for its flexibility, corrosion resistance, and tensile strength, making it an ideal carrier material for photocatalysts. In addition, its excellent conductivity enhances the rapid transfer of photogenerated electrons, improving photocatalytic performance. In previous studies, we successfully synthesized CF/SrTiO3 composite fiber materials and demonstrated that doping with Mn or incorporating CdS enhances light absorption and photogenerated electron transport, thereby improving the photocatalytic performance and facilitating the recyclability of the composite [10,11]. In this work, CF/SrTiO3 composite fiber material was employed as a substrate for the initial deposition of In seeds. Subsequently, a double-layer core–shell-structured CF/SrTiO3/In2O3 photocatalytic composite fiber material was synthesized via a solvothermal method that enabled in situ growth. The enhancement mechanism of the CF/SrTiO3/In2O3 composite fiber material in photocatalytic water-splitting hydrogen evolution was further discussed.

2. Experimental

2.1. Materials and Main Equipment

Strontium acetate (C4H6O4Sr, 99%) was obtained from Aladdin Reagent Co., Ltd. (Shanghai, China). Titanium (IV) isopropoxide (C12H28O4Ti, 97%), indium trichloride (InCl3, 99.99%), and Indium (III) nitrate hydrate (In(NO3)3·4.5H2O, 99.5%) were obtained from Sinopharm Chemical Reagent Co., Ltd. China. Tencel fibers were supplied by Lenzing Fibers Co., Ltd. (Nanjing, Jiangsu Province, China), with a linear density of 1.4dtex with 38 mm.
The heating and drying oven (DHG-9030A) was bought from Shanghai Jinghong Laboratory Instrument Co., Ltd. (Shanghai, China). The tube furnace (OTF-1200X-50) was bought from Hefei Kejing materials Technology Co., Ltd. (Hefei, China).

2.2. Preparation of CF/SrTiO3/In2O3 Composite Material

The CF/SrTiO3 composite fiber, featuring a core–shell heterojunction structure, was prepared using the method outlined in previous studies [10,11]. Generally, this involves coating a SrTiO3 nanolayer onto Tencel fibers via the solvothermal method at 180 °C for 7 h, followed by carbonizing the fibers at 800 °C for 2 h under nitrogen to form CF/SrTiO3.
CF/SrTiO3–In seed composite fibers were produced based on the seed growth method previously used for coating Bi2O3 nanomaterial onto carbon fibers [12]. Specifically, an InCl3/ethanol solution was prepared by dissolving 0.4 g of InCl3 in 40 mL of ethanol, followed by 5 min of sonication and 30 min of stirring. The CF/SrTiO3 composite fibers were immersed in this solution for 3 h, followed by a 3 h drying period, and subsequently subjected to heating in a muffle furnace at 300 °C for 6 min to obtain CF/SrTiO3–In seed composite fibers.
CF/SrTiO3/In2O3 composite fibers were then fabricated via the solvothermal method via in situ growth on the CF/SrTiO3–In seed composite fibers. In this process, 0.33 g of InNO3 was added into a mixed solution of 15 mL of ethanol and 20 mL of glycol, and the mixture was stirred for 30 min to obtain a homogenous solution. The above-mentioned CF/SrTiO3–In seed composite fibers were added to the mixture and transferred into a polytetrafluoroethylene reactor for solvothermal reaction at 180 °C for 20 h [13,14]. Afterward, the composite was cleaned with absolute ethyl alcohol and dried in an oven at 60 °C for 24 h, resulting in the formation of CF/SrTiO3/In2O3 composite fibers. The detailed preparation process is demonstrated in Figure 1.

2.3. Characterization Method

An X-ray diffractometer (XRD, Bruker D8 Disvover, Bruker, Karlsruhe, Germany) with a scanning speed of 0.2°/min was used to characterize the crystalline structures of the as-prepared samples. The morphologies of the samples were examined using a scanning electron microscope (FESEM Hitachi S-4800, Tokyo, Japan) and a transmission electron microscope (TEM FEI Talos F200x G2, FEI Company, Hillsboro, OR, USA). X-ray photoelectron spectroscopy (XPS) measurement was carried out using a Thermo Scientific K-Alpha spectrometer. An electronic paramagnetic spectrometer (EPR, Bruker EMX PLUS, Bruker, Karlsruhe, Germany) with a sweep width of 100 G was used to assess the defects in the samples. Electrochemical properties were also tested using an electrochemical workstation (CHI660E, Shanghai Chenhua Instrumental Co., Ltd., Shanghai, China) by applying the standard three-electrode testing method. A Hitachi F-7000 spectrophotometer was used to measure the light absorption response range of the samples.

2.4. Photocatalytic Evolution

A gas chromatograph (GC-7900, Techcomp (China) Co., Ltd., Shanghai, China) was used to identify the photocatalytic hydrogen evolution performance. For each test, 100 mg of photocatalyst was used. Na2S and Na2SO3 served as sacrificial agents, and the reaction took place in 100 mL of aqueous solution. A 300 W xenon lamp (PLS-SE300C, Beijing perfectlight Co., Ltd., Beijing, China) was utilized to simulate sunlight [10,11].

3. Results and Discussion

The CF/SrTiO3/In2O3 composite fibers with a double-layer core–shell structure were produced via an in situ seed growth method. The XRD patterns of CF/SrTiO3/In2O3, CF/SrTiO3, SrTiO3, and CF are shown in Figure 2. The characteristic diffraction peaks observed in both the CF/SrTiO3 composite and CF/SrTiO3/In2O3 composite correspond to JCPDS# 35-0734 on the XRD standard card, confirming the presence of a cubic phase perovskite structure of SrTiO3 on the surface of the carbon fibers [15]. However, the XRD spectra of the CF/SrTiO3/In2O3 composite fibers show no significant diffraction peaks attributable to In2O3, such as a signal near 30.6° [16]. This absence may be due to the use of glycol as a solvent. Moreover, the mass of both the CF/SrTiO3/In2O3 composite and the CF/SrTiO3 was measured. The CF/SrTiO3/In2O3 composite exhibited only a 10% increase in mass compared to the CF/SrTiO3 material, suggesting a relatively low content of In2O3. These findings indicate a need for further characterization to confirm the presence of In2O3 in the composites.
The SEM images of Tencel fibers, CF/SrTiO3 composite fibers, and CF/SrTiO3/In2O3 composite fibers are shown in Figure 3. Figure 3a presents Tencel fibers with a smooth surface, and each fiber shows a diameter of about 10 µm. Figure 3b,c reveal that the SrTiO3 material layer is coated on the carbon fibers, with the diameter reduced to 6–7 µm. The reduction is probably caused by the high-temperature carbonization [17]. Figure 3b,c also show that the SrTiO3 material layer is composed of nanoparticles with a cubic phase structure, which are closely bonded to form a continuous coating layer. Figure 3d,e illustrate that the In2O3 material layer, prepared using the solvothermal method and applied like a paste, covers the CF/SrTiO3 composite fibers. This layer features a nanosheet structure that resembles a ceramic tile covering [18]. The cross-section of the CF/SrTiO3/In2O3 composite fiber is displayed in Figure 3f, where the SrTiO3/In2O3 material layer is applied to the carbon fibers’ surface, with In2O3 nanosheets forming the outermost layer.
The elemental distribution of the CF/SrTiO3/In2O3 composite fibers was analyzed using SEM mapping, as depicted in Figure 4. It demonstrated a homogeneous distribution of O, Sr, Ti, and In on the surface of the composite fibers. Additionally, it can be noticed that in Figure 4b, the C signal in the CF/SrTiO3/In2O3 composite fibers seems relatively weak, but the signals on the periphery are relatively strong. This is because SEM mapping is mainly used to detect the elemental distribution on the surface of the material, but CF located in the core of the composite fiber is covered by SrTiO3/In2O3, and the C element around the fiber comes from the carbon conductive adhesive on the SEM stub.
The microstructure of the composite material was further observed by the transmission electron microscopy. Figure 5 presents TEM and HRTEM images of the SrTiO3/In2O3, which was ultrasonically stripped from the surface of the CF/SrTiO3/In2O3 composite fibers. The interplanar spacing observed in Figure 5c is about 0.297 nm, corresponding to the (222) crystal face of In2O3 (JCPDS# 06–0416) [19]. This confirms the successful loading of In2O3 nanosheets onto the surface of the CF/SrTiO3 composite fibers and the formation of a heterojunction structure between SrTiO3 and In2O3. Figure 5d shows an interplanar spacing of approximately 0.278 nm, matching the (110) crystal face of SrTiO3 (JCPDS# 35-0734) [20,21]. Additionally, a double-layer structure can be seen in Figure 5a, where the upper layer mainly comprises SrTiO3 nanoparticles, and the lower layer consists of In2O3 nanosheets approximately 35 nm wide. These observations, in conjunction with Figure 3, all prove that the CF/SrTiO3/In2O3 composite fibers possess a double-layer core–shell structure.
Figure 6 shows the TEM EDS diagram of the nanosheet material obtained from the surface of the carbon fibers after ultrasonic treatment of the CF/SrTiO3/In2O3 composite fibers. The diagram also reveals a uniform distribution of In, Sr, Ti, and O elements throughout the material, suggesting that SrTiO3 and In2O3 are evenly dispersed and form a homogeneous heterojunction structure.
Qualitative and valence analysis of the elements on the surface of the CF/SrTiO3/In2O3 composite fibers was performed using X-ray photoelectron spectroscopy (XPS). Figure 7a shows a typical wide-scan spectrum of the CF/SrTiO3/In2O3 composite fibers, which includes five elements: C, Sr, Ti In, and O. The signals of the In and O exhibit a comparatively high intensity, while the signals of the C, Sr, and Ti have a relatively low intensity. This is mainly due to the double-layer core–shell structure of the CF/SrTiO3/In2O3 composite, in which the In2O3 is situated in the outermost layer, and CF/SrTiO3 forms the inner layer. As illustrated in Figure 7b, two characteristic peaks at the binding energies of 284.3 eV and 285.8 eV are identified in the C 1s spectrum, which corresponds to the C-C bond and C-O bond, respectively [22]. Figure 7c reveals the presence of three peaks in the O 1s high-resolution XPS spectrum. The peak observed at a binding energy of 529.8 eV corresponds to lattice oxygen in SrTiO3. On the other hand, the peak at 531.6 eV may indicate the presence of adsorption oxygen in oxygen vacancies, whereas the peak at 532.4 eV is associated with surface adsorption oxygen. And the highest peak at 531.6 eV indicates a significant abundance of oxygen vacancies in the CF/SrTiO3/In2O3 material [23,24,25]. Figure 7d shows the peaks in the Ti 2p spectrum that have been fitted. The peaks at binding energies of 458.7 eV and 464.6 eV correspond to the characteristic peaks of Ti 2p3/2 and Ti 2p1/2, respectively, with a difference of 5.9 eV between them, representing the presence of Ti4+ ions [26,27]. Additionally, the peaks at binding energies of 458.2 eV and 464.1 eV are probably related to Ti3+ ions.
Figure 7e illustrates four characteristic peaks in the In 3d spectrum, located at binding energies of 448.0 eV and 455.6 eV, corresponding to the In 3d5/2 and In 3d3/2 peaks of In3+ ions, with a difference of 7.6 eV between the two peaks [28,29]. Moreover, these peaks suggest the presence of oxygen vacancies, which may cause a reduction in the valence of In3+ ions, potentially to states between 0 and 2+ [30]. Figure 7f shows the characteristic peaks in the Sr 3d spectrum at binding energies of 133.2 eV and 135.0 eV, attributed to Sr 3d5/2 and Sr 3d3/2, respectively, with a 1.8 eV difference between them, indicating a Sr ion valence of +2 [31].
To further verify the existence of oxygen vacancies in the CF/SrTiO3/In2O3 composite fibers, an EPR test was conducted, as shown in Figure 8. This test reveals a strong signal at g ≈ 2.003, which is indicative of the existence of oxygen vacancies in the material [32]. The use of 20 mL of glycol as a solvent and the deposition of In2O3 on the CF/SrTiO3 fibers likely contributed to a high concentration of oxygen vacancies within the In2O3 [33]. And previous studies have indicated that the SrTiO3 in the CF/SrTiO3 composite fibers also contains oxygen vacancies [10]. Hence, it can be deduced that the oxygen vacancies in the CF/SrTiO3/In2O3 composite fibers originate from both the SrTiO3 and In2O3 components, which are believed to significantly improve the photocatalytic performance of the composite material.
The mass composition of SrTiO3/In2O3 in the CF/SrTiO3/In2O3 composite fiber material was determined using a TG test conducted in an air atmosphere, as seen in Figure 9. The result indicates a gradual weight loss occurring between 100 °C and 420 °C, followed by a rapid weight loss between 420 °C and 550 °C, likely due to the combustion decomposition of the carbon fiber component. It is estimated that SrTiO3/In2O3 constitutes approximately 48% of the composite fiber material, given that the final weight loss in air conditions is approximately 52%.
The photocatalytic water-splitting hydrogen evolution performance was evaluated using a 300 W xenon lamp to simulate sunlight, with the findings presented in Figure 10. The CF/SrTiO3 sample exhibited a hydrogen evolution rate of about 45.18 μmol/g·h, whereas the CF/SrTiO3/In2O3 sample showed a rate of approximately 320.71 μmol/g·h, nearly 7 times higher than that of the CF/SrTiO3 sample. The significant enhancement can be attributed to the wider band gap of In2O3, which, even as a minor coating of nanosheets on the CF/SrTiO3 fibers, markedly improves photocatalytic performance [34]. It is apparent that CF alone does not contribute to photocatalytic hydrogen evolution under light, suggesting that the performances of both CF/SrTiO3 and CF/SrTiO3/In2O3 composites are primarily influenced by the SrTiO3 and In2O3 components. However, the excellent electrical conductivity of the carbon fibers promotes the separation, generation, and migration of photogenerated electron–hole pairs within these materials, thus enhancing their photocatalytic activity [35]. In addition, the presence of abundant oxygen vacancies in the CF/SrTiO3/In2O3 composite fiber material may also contribute to its improved performance.
The photocatalytic hydrogen evolution cyclic stability of the CF/SrTiO3/In2O3 composite fiber material was also measured, as shown in Figure 11. After four consecutive cyclic tests for photocatalytic water-splitting hydrogen evolution, the CF/SrTiO3/In2O3 composite fibers maintained an average hydrogen evolution performance of approximately 268 μmol/g·h, with no significant loss of activity observed. This indicates that the CF/SrTiO3/In2O3 composite catalyst possesses robust photocatalytic stability during the water-splitting hydrogen evolution process.
Figure 12 presents the electrochemical impedance diagram of CF, CF/SrTiO3, and CF/SrTiO3/In2O3 photocatalytic composite fiber materials. Among these three materials, the CF/SrTiO3/In2O3 composite displays the smallest first arc radius in the EIS, indicating higher charge mobility and faster separation of photoelectrons and holes, which implies lower resistance and higher photocatalytic activity [36,37]. These observations are in agreement with prior experimental results from photocatalytic hydrogen evolution studies.
The absorption response range of a photocatalyst to light is crucial for its photocatalytic activity. Figure 13 shows the UV-Vis diffuse reflection spectra of CF/SrTiO3, CF/SrTiO3/In2O3, CF, and SrTiO3. It can be seen that the pure SrTiO3 sample exhibits a characteristic light absorption band edge near 375 nm, while the CF/SrTiO3 photocatalytic fiber sample shows a broader light absorption range. This may be attributed to the strong light absorption properties of carbon fibers. The band gap of the pure In2O3 sample is approximately 2.8 eV [38]. Consequently, after coating the CF/SrTiO3 composite fibers with a thin layer of In2O3 nanosheets, the light absorption band edge of the CF/SrTiO3/In2O3 sample demonstrates a red shift toward visible light compared to the CF/SrTiO3 sample.
According to our previous study [10], the band gap of the pure SrTiO3 sample is 3.32 eV, with a conduction band position at −0.55 eV and a valence band position at 2.77 eV. And it was reported that the band gap of the In2O3 material is about 2.77 eV, with a conduction band position of around −0.62 eV and a valence band position of 2.15 eV [39]. Both SrTiO3 and In2O3 materials in the CF/SrTiO3/In2O3 composite fiber exhibit numerous oxygen vacancies, as confirmed by this work and previously published XPS and EPR tests [10]. The presence of these oxygen vacancies introduces a new donor level below the conduction band, forming an oxygen vacancy state (VOs). This state not only reduces the band gap and extends the light absorption boundary of the material but also serves as a trap for photogenerated electrons, enhancing the separation of electron–hole pairs and inhibiting their recombination [40,41,42].
Based on these insights, we propose a mechanism for the photocatalytic water-splitting hydrogen evolution in the CF/SrTiO3/In2O3 composite fiber material, as illustrated in Figure 14. Since the conduction and valence band positions of pure In2O3 are higher than those of SrTiO3, photogenerated electrons migrate from the conduction band of the In2O3 nanosheets to that of the SrTiO3 nanomaterial, while photogenerated holes move rapidly from the conduction band of SrTiO3 to the valence band of In2O3 nanosheets. The excellent conductivity of carbon fibers allows photogenerated electrons on SrTiO3 to migrate to the carbon fiber surface, thereby inhibiting the recombination of the photogenerated electron–hole pairs. The presence of the VOs creates a trap for photogenerated electrons, facilitating their movement from the In2O3 nanosheets to the surface oxygen vacancy state and promoting the reduction of H+ in water to evolve hydrogen [43]. In addition, holes on the surface of SrTiO3 are readily captured by sacrificial agents (Na2S and Na2SO3) in the aqueous solution, promoting the generation and separation of photogenerated electron–hole pairs and facilitating the water-splitting hydrogen evolution process of the catalyst [44].

4. Conclusions

In this study, CF/SrTiO3/In2O3 composite fibers were fabricated as a photocatalytic material. Initially, Tencel fibers were coated with a SrTiO3 layer, and after carbonization, CF/SrTiO3 was produced. Subsequently, In seeds were deposited onto this substrate using an immersion heating method, and the final composite fiber was synthesized via a solvothermal method employing in situ growth on the CF/SrTiO3–In seed composite fibers. This process resulted in the formation of a SrTiO3/In2O3 heterojunction on the carbon fibers. XPS and EPR measurements suggested the presence of oxygen vacancies in both the SrTiO3 and In2O3 materials within the composite fibers. Under simulated sunlight using a xenon lamp, the photocatalytic hydrogen evolution rate of the CF/SrTiO3/In2O3 fibers reached approximately 320.71 μmol/g·h, about seven times higher than that of CF/SrTiO3. Subsequent cyclic tests confirmed the robust photocatalytic stability of the CF/SrTiO3/In2O3 fibers. The mechanism can be explained by the presence of oxygen vacancies, which, along with the material’s heterojunction structure and the carbon fibers’ superior electrical conductivity, significantly enhance the separation, generation, and migration of photogenerated electrons. This improvement not only promotes photocatalytic activity but also reduces the recombination of electron–hole pairs, ultimately boosting photocatalytic hydrogen evolution performance in these fibers.
This study established a reference method for preparing photocatalytic composite materials using an in situ seed growth approach on carbon fibers. Furthermore, it opens up possibilities for exploring the use of carbon fiber-based photocatalytic composites as raw materials for constructing network materials via techniques such as knitting or bonding, potentially enabling the recycling of nanometer-scale photocatalysts and thereby boosting environmental sustainability and material efficiency.

Author Contributions

Conceptualization, Q.H. and J.N.; Data curation, Q.H. and J.N.; Funding acquisition, J.N.; Investigation, Q.H. and J.N.; Methodology, Q.H., J.N.; Supervision, Q.H.; Writing—original draft, Q.H.; Writing—review & editing, J.N. All authors have read and agreed to the published version of the manuscript.

Funding

This research was supported in part by the Natural Science Foundation of Jiangsu Province (BK20231205), and in part by the “Qinglan Project” of Jiangsu Province in China under Grant 2024.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Data are contained within the article.

Conflicts of Interest

The authors declare no conflicts of interest.

References

  1. Fujishima, A.; Honda, K. Electrochemical photolysis of water at a semiconductor electrode. Nature 1972, 238, 37–38. [Google Scholar] [CrossRef] [PubMed]
  2. Zhang, F.; Wang, X.; Liu, H.; Liu, C.; Wan, Y.; Long, Y.; Cai, Z. Recent advances and applications of semiconductor photocatalytic technology. Appl. Sci. 2019, 9, 2489. [Google Scholar] [CrossRef]
  3. Lakhera, S.K.; Rajan, A.; Rugma, T.; Bernaurdshaw, N. A review on particulate photocatalytic hydrogen production system: Progress made in achieving high energy conversion efficiency and key challenges ahead. Renew. Sustain. Energy Rev. 2021, 152, 111694. [Google Scholar] [CrossRef]
  4. Han, L.; Jing, F.; Luo, X.-Z.; Zhong, Y.-L.; Wang, K.; Zang, S.-H.; Teng, D.-H.; Liu, Y.; Chen, J.; Yang, C. Environment friendly and remarkably efficient photocatalytic hydrogen evolution based on metal organic framework derived hexagonal/cubic In2O3 phase-junction. Appl. Catal. B Environ. 2021, 282, 119602. [Google Scholar] [CrossRef]
  5. Martha, S.; Reddy, K.H.; Parida, K. Fabrication of In2O3 modified ZnO for enhancing stability, optical behaviour, electronic properties and photocatalytic activity for hydrogen production under visible light. J. Mater. Chem. A 2014, 2, 3621–3631. [Google Scholar] [CrossRef]
  6. Liu, M.; Li, P.; Wang, S.; Liu, Y.; Zhang, J.; Chen, L.; Wang, J.; Liu, Y.; Shen, Q.; Qu, P. Hierarchically porous hydrangea-like In2S3/In2O3 heterostructures for enhanced photocatalytic hydrogen evolution. J. Colloid Interface Sci. 2021, 587, 876–882. [Google Scholar] [CrossRef] [PubMed]
  7. Hato, T.; Takauchi, H.; Yoshida, A.; Tamura, H.; Fujimaki, N.; Oshima, Y.; Yokoyama, N.Y.N. Improved emitter-base junction with In2O3 in dielectric-base transistor. Jpn. J. Appl. Phys. 1995, 34, 6379. [Google Scholar] [CrossRef]
  8. Hato, T.; Yoshida, A.; Yoshida, C.; Suzuki, H.; Yokoyama, N. Dielectric-base transistors with doped channel. Appl. Phys. Lett. 1997, 70, 2900–2902. [Google Scholar] [CrossRef]
  9. Liang, Y.-C.; Huang, C.-L.; Hu, C.-Y. Effects of growth temperature on structure and electrical properties of dielectric (Ba, Sr) TiO3 capacitors with transparent conducting oxide electrodes. J. Alloys Compd. 2011, 509, 7948–7952. [Google Scholar] [CrossRef]
  10. Hu, Q.; Niu, J.; Zhang, K.-Q.; Yao, M. Fabrication of Mn-doped SrTiO3/carbon fiber with oxygen vacancy for enhanced photocatalytic hydrogen evolution. Materials 2022, 15, 4723. [Google Scholar] [CrossRef]
  11. Hu, Q.; Niu, J.; Zhang, K.-Q.; Yao, M. One-Dimensional CdS/SrTiO3/Carbon Fiber Core–Shell Photocatalysts for Enhanced Photocatalytic Hydrogen Evolution. Coatings 2022, 12, 1235. [Google Scholar] [CrossRef]
  12. Liu, S.; Lu, X.F.; Xiao, J.; Wang, X.; Lou, X.W. Bi2O3 nanosheets grown on multi-channel carbon matrix to catalyze efficient CO2 electroreduction to HCOOH. Angew. Chem. 2019, 131, 13966–13971. [Google Scholar] [CrossRef]
  13. Gao, B.; Wan, J.; Hu, D.; Chen, Y.; Lin, B. Enhanced visible-light-driven photocatalytic performance of In2O3-loaded TiO2 nanocubes with exposed (001) facet. Chem. Res. Chin. Univ. 2017, 33, 934–938. [Google Scholar] [CrossRef]
  14. Sariket, D.; Shyamal, S.; Hajra, P.; Mandal, H.; Bera, A.; Maity, A.; Bhattacharya, C. Improvement of photocatalytic activity of surfactant modified In2O3 towards environmental remediation. New J. Chem. 2018, 42, 2467–2475. [Google Scholar] [CrossRef]
  15. Yu, K.; Zhang, C.; Chang, Y.; Feng, Y.; Yang, Z.; Yang, T.; Lou, L.-L.; Liu, S. Novel three-dimensionally ordered macroporous SrTiO3 photocatalysts with remarkably enhanced hydrogen production performance. Appl. Catal. B Environ. 2017, 200, 514–520. [Google Scholar] [CrossRef]
  16. Li, H.; Sun, T.; Zhang, L.; Cao, Y. Improved photocatalytic activity of ZnO via the modification of In2O3 and MoS2 surface species for the photoreduction of CO2. Appl. Surf. Sci. 2021, 566, 150649. [Google Scholar] [CrossRef]
  17. Kim, H.G.; Kim, Y.-S.; Kuk, Y.-S.; Kwac, L.K.; Choi, S.-H.; Park, J.; Shin, H.K. Preparation and Characterization of Carbon Fibers from Lyocell Precursors Grafted with Polyacrylamide via Electron-Beam Irradiation. Molecules 2021, 26, 2459. [Google Scholar] [CrossRef] [PubMed]
  18. Gao, L.; Cheng, Z.; Xiang, Q.; Zhang, Y.; Xu, J. Porous corundum-type In2O3 nanosheets: Synthesis and NO2 sensing properties. Sens. Actuators B Chem. 2015, 208, 436–443. [Google Scholar] [CrossRef]
  19. Liu, X.; Xu, B.; Duan, X.; Hao, Q.; Wei, W.; Wang, S.; Ni, B.-J. Facile preparation of hydrophilic In2O3 nanospheres and rods with improved performances for photocatalytic degradation of PFOA. Environ. Sci. Nano 2021, 8, 1010–1018. [Google Scholar] [CrossRef]
  20. Chen, Z.; Pan, J.; Mei, J.; Yu, Q.; Wang, P.; Wang, P.; Wang, J.; Song, C.; Zheng, Y.; Li, C. Ternary Co3O4/CdS/SrTiO3 core-shell pn junctions toward enhanced photocatalytic hydrogen production activity. J. Environ. Chem. Eng. 2021, 9, 104895. [Google Scholar] [CrossRef]
  21. Zhao, Y.; Guo, Y.; Li, J.; Li, P. Efficient hydrogen evolution with ZnO/SrTiO3 S-scheme heterojunction photocatalyst sensitized by Eosin Y. Int. J. Hydrogen Energy 2021, 46, 18922–18935. [Google Scholar] [CrossRef]
  22. Chen, X.; Wang, X.; Fang, D. A review on C1s XPS-spectra for some kinds of carbon materials. Fuller. Nanotub. Carbon Nanostructures 2020, 28, 1048–1058. [Google Scholar] [CrossRef]
  23. Al-Hashem, M.; Akbar, S.; Morris, P. Role of oxygen vacancies in nanostructured metal-oxide gas sensors: A review. Sens. Actuators B Chem. 2019, 301, 126845. [Google Scholar] [CrossRef]
  24. Huang, Y.; Yu, Y.; Yu, Y.; Zhang, B. Oxygen vacancy engineering in photocatalysis. Sol. RRL 2020, 4, 2000037. [Google Scholar] [CrossRef]
  25. Fan, Y.; Liu, Y.; Cui, H.; Wang, W.; Shang, Q.; Shi, X.; Cui, G.; Tang, B. Photocatalytic Overall Water Splitting by SrTiO3 with Surface Oxygen Vacancies. Nanomaterials 2020, 10, 2572. [Google Scholar] [CrossRef] [PubMed]
  26. Thakur, P.; Tan, B.; Venkatakrishnan, K. Multi-phase functionalization of titanium for enhanced photon absorption in the vis-NIR region. Sci. Rep. 2015, 5, 15354. [Google Scholar] [CrossRef] [PubMed]
  27. Hara, T.; Ishiguro, T.; Shinozaki, K. Annealing effects on sensitivity of atomic-layer-deposited SrTiO3-based oxygen sensors. Jpn. J. Appl. Phys. 2010, 49, 09MA15. [Google Scholar] [CrossRef]
  28. Wang, Y.-C.; Sun, Z.-S.; Wang, S.-Z.; Wang, S.-Y.; Cai, S.-X.; Huang, X.-Y.; Li, K.; Chi, Z.-T.; Pan, S.-D.; Xie, W.-F. Sub-ppm acetic acid gas sensor based on In2O3 nanofibers. J. Mater. Sci. 2019, 54, 14055–14063. [Google Scholar] [CrossRef]
  29. Liu, M.; Wang, Z.; Song, P.; Yang, Z.; Wang, Q. In2O3 nanocubes/Ti3C2Tx MXene composites for enhanced methanol gas sensing properties at room temperature. Ceram. Int. 2021, 47, 23028–23037. [Google Scholar] [CrossRef]
  30. Bronsato, B.J.d.S.; Zonetti, P.C.; Moreira, C.R.; Mendoza, C.D.; da Costa, M.E.M.; Alves, O.C.; de Avillez, R.R.; Appel, L.G. How the interaction between In2O3-ZrO2 promotes the isobutene synthesis from ethanol? Catal. Today 2021, 381, 224–233. [Google Scholar] [CrossRef]
  31. Tanguturi, R.G.; Zhou, P.; Yan, Z.; Qi, Y.; Xia, Z.; Liu, Y.; Xiong, R.; Guo, Y.; Wang, L.; Srinivasan, G. Study of Electronic States in LaNiO3/SrRuO3 Bilayers: Interface-Induced Magnetism and Charge Transfer. Phys. Status Solidi 2021, 258, 2000527. [Google Scholar] [CrossRef]
  32. Ji, Q.; Bi, L.; Zhang, J.; Cao, H.; Zhao, X.S. The role of oxygen vacancies of ABO3 perovskite oxides in the oxygen reduction reaction. Energy Environ. Sci. 2020, 13, 1408–1428. [Google Scholar] [CrossRef]
  33. Garcia, L.; Tavares, M.; Andrade Neto, N.; Nascimento, R.; Paskocimas, C.; Longo, E.; Bomio, M.; Motta, F. Photocatalytic activity and photoluminescence properties of TiO2, In2O3, TiO2/In2O3 thin films multilayer. J. Mater. Sci. Mater. Electron. 2018, 29, 6530–6542. [Google Scholar] [CrossRef]
  34. Duan, Y.; Xue, J.; Dai, J.; Wei, Y.; Wu, C.; Chang, S.-H.; Ma, J. Interface engineering of ZnO/In2O3 Z-scheme heterojunction with yolk-shell structure for efficient photocatalytic hydrogen evolution. Appl. Surf. Sci. 2022, 596, 153306. [Google Scholar] [CrossRef]
  35. Yu, Z.; Meng, J.; Li, Y.; Li, Y. Efficient photocatalytic hydrogen production from water over a CuO and carbon fiber comodified TiO2 nanocomposite photocatalyst. Int. J. Hydrogen Energy 2013, 38, 16649–16655. [Google Scholar] [CrossRef]
  36. Mallikarjuna, A.; Ramesh, S.; Kumar, N.S.; Naidu, K.C.B.; Ratnam, K.V.; Manjunatha, H. Photocatalytic Activity, Negative AC-Electrical Conductivity, Dielectric Modulus, and Impedance Properties in 0.6 (Al0.2La0.8TiO3)+ 0.4 (BiFeO3) Nanocomposite. Cryst. Res. Technol. 2020, 55, 2000068. [Google Scholar] [CrossRef]
  37. Liu, X.; Xu, S.; Chi, H.; Xu, T.; Guo, Y.; Yuan, Y.; Yang, B. Ultrafine 1D graphene interlayer in g-C3N4/graphene/recycled carbon fiber heterostructure for enhanced photocatalytic hydrogen generation. Chem. Eng. J. 2019, 359, 1352–1359. [Google Scholar] [CrossRef]
  38. Zhou, P.; Meng, X.; Sun, T. Facile fabrication of In2O3/S-doped g-C3N4 heterojunction hybrids for enhanced visible-light photocatalytic hydrogen evolution. Mater. Lett. 2020, 261, 127159. [Google Scholar] [CrossRef]
  39. Xu, H.; Wang, Y.; Dong, X.; Zheng, N.; Ma, H.; Zhang, X. Fabrication of In2O3/In2S3 microsphere heterostructures for efficient and stable photocatalytic nitrogen fixation. Appl. Catal. B: Environ. 2019, 257, 117932. [Google Scholar] [CrossRef]
  40. Li, J.; Zhang, M.; Guan, Z.; Li, Q.; He, C.; Yang, J. Synergistic effect of surface and bulk single-electron-trapped oxygen vacancy of TiO2 in the photocatalytic reduction of CO2. Appl. Catal. B Environ. 2017, 206, 300–307. [Google Scholar] [CrossRef]
  41. Hou, L.; Zhang, M.; Guan, Z.; Li, Q.; Yang, J. Effect of annealing ambience on the formation of surface/bulk oxygen vacancies in TiO2 for photocatalytic hydrogen evolution. Appl. Surf. Sci. 2018, 428, 640–647. [Google Scholar] [CrossRef]
  42. Li, J.-J.; Weng, B.; Cai, S.-C.; Chen, J.; Jia, H.-P.; Xu, Y.-J. Efficient promotion of charge transfer and separation in hydrogenated TiO2/WO3 with rich surface-oxygen-vacancies for photodecomposition of gaseous toluene. J. Hazard. Mater. 2018, 342, 661–669. [Google Scholar] [CrossRef]
  43. Wang, H.; Yong, D.; Chen, S.; Jiang, S.; Zhang, X.; Shao, W.; Zhang, Q.; Yan, W.; Pan, B.; Xie, Y. Oxygen-vacancy-mediated exciton dissociation in BiOBr for boosting charge-carrier-involved molecular oxygen activation. J. Am. Chem. Soc. 2018, 140, 1760–1766. [Google Scholar] [CrossRef]
  44. Huang, H.-B.; Fang, Z.-B.; Yu, K.; Lü, J.; Cao, R. Visible-light-driven photocatalytic H2 evolution over CdZnS nanocrystal solid solutions: Interplay of twin structures, sulfur vacancies and sacrificial agents. J. Mater. Chem. A 2020, 8, 3882–3891. [Google Scholar] [CrossRef]
Figure 1. Flow chart of preparation process of CF/SrTiO3/In2O3 photocatalytic composite fibers.
Figure 1. Flow chart of preparation process of CF/SrTiO3/In2O3 photocatalytic composite fibers.
Sustainability 16 03988 g001
Figure 2. XRD pattern of CF/SrTiO3/In2O3, CF/SrTiO3, SrTiO3, and carbon fiber (CF) samples.
Figure 2. XRD pattern of CF/SrTiO3/In2O3, CF/SrTiO3, SrTiO3, and carbon fiber (CF) samples.
Sustainability 16 03988 g002
Figure 3. SEM diagram of samples, (a) Tencel fiber, (b,c) CF/SrTiO3, and (df) CF/SrTiO3/In2O3.
Figure 3. SEM diagram of samples, (a) Tencel fiber, (b,c) CF/SrTiO3, and (df) CF/SrTiO3/In2O3.
Sustainability 16 03988 g003
Figure 4. SEM mapping diagram of CF/SrTiO3/In2O3 sample, (a) SEM diagram of composite fiber, (b) C element, (c) O element, (d) Sr element, (e) Ti element, (f) In element, and (g) element content diagram.
Figure 4. SEM mapping diagram of CF/SrTiO3/In2O3 sample, (a) SEM diagram of composite fiber, (b) C element, (c) O element, (d) Sr element, (e) Ti element, (f) In element, and (g) element content diagram.
Sustainability 16 03988 g004
Figure 5. TEM diagram of CF/SrTiO3/In2O3 sample, (a) SrTiO3/In2O3 nanosheets, (b) HRTEM at interface, (c) HRTEM of In2O3, and (d) HRTEM of SrTiO3.
Figure 5. TEM diagram of CF/SrTiO3/In2O3 sample, (a) SrTiO3/In2O3 nanosheets, (b) HRTEM at interface, (c) HRTEM of In2O3, and (d) HRTEM of SrTiO3.
Sustainability 16 03988 g005
Figure 6. TEM EDS diagram of CF/SrTiO3/In2O3 sample: (a) SEM diagram of nanosheets peeled off from composite fibers, (b) In element, (c) O element, (d) Sr element, (e) Ti element, and (f) Multi-element.
Figure 6. TEM EDS diagram of CF/SrTiO3/In2O3 sample: (a) SEM diagram of nanosheets peeled off from composite fibers, (b) In element, (c) O element, (d) Sr element, (e) Ti element, and (f) Multi-element.
Sustainability 16 03988 g006
Figure 7. XPS diagram of CF/SrTiO3/In2O3 sample, (a) full spectrum, (b) C 1s spectrum, (c) O 1s spectrum, (d) Ti 2p spectrum, (e) In 3d spectrum, and (f) Sr 3d spectrum. In subfigures (bf), the black curve are experimental data, the red curve is the fitting of the fitting peak data, and the blue curve is the background from the simulation.
Figure 7. XPS diagram of CF/SrTiO3/In2O3 sample, (a) full spectrum, (b) C 1s spectrum, (c) O 1s spectrum, (d) Ti 2p spectrum, (e) In 3d spectrum, and (f) Sr 3d spectrum. In subfigures (bf), the black curve are experimental data, the red curve is the fitting of the fitting peak data, and the blue curve is the background from the simulation.
Sustainability 16 03988 g007
Figure 8. EPR test of CF/SrTiO3/In2O3 composite fiber material.
Figure 8. EPR test of CF/SrTiO3/In2O3 composite fiber material.
Sustainability 16 03988 g008
Figure 9. TG curve of CF/SrTiO3/In2O3 composite fiber material.
Figure 9. TG curve of CF/SrTiO3/In2O3 composite fiber material.
Sustainability 16 03988 g009
Figure 10. Photocatalytic hydrogen evolution rate (a) and time-dependent hydrogen evolution amount (b) of CF/SrTiO3/In2O3, CF/SrTiO3, and CF samples.
Figure 10. Photocatalytic hydrogen evolution rate (a) and time-dependent hydrogen evolution amount (b) of CF/SrTiO3/In2O3, CF/SrTiO3, and CF samples.
Sustainability 16 03988 g010
Figure 11. Photocatalytic stability diagram of CF/SrTiO3/In2O3 composite fiber material, (a) corresponding histogram of hydrogen evolution rate, and (b) cycle curve of hydrogen evolution amount.
Figure 11. Photocatalytic stability diagram of CF/SrTiO3/In2O3 composite fiber material, (a) corresponding histogram of hydrogen evolution rate, and (b) cycle curve of hydrogen evolution amount.
Sustainability 16 03988 g011
Figure 12. Electrochemical impedance spectra of CF/SrTiO3/In2O3, CF/SrTiO3, and CF.
Figure 12. Electrochemical impedance spectra of CF/SrTiO3/In2O3, CF/SrTiO3, and CF.
Sustainability 16 03988 g012
Figure 13. UV-Vis diffuse reflection spectra of CF/SrTiO3/In2O3, CF/SrTiO3, SrTiO3, and CF.
Figure 13. UV-Vis diffuse reflection spectra of CF/SrTiO3/In2O3, CF/SrTiO3, SrTiO3, and CF.
Sustainability 16 03988 g013
Figure 14. Photocatalytic hydrogen evolution mechanism of CF/SrTiO3/In2O3 photocatalytic composite fibers.
Figure 14. Photocatalytic hydrogen evolution mechanism of CF/SrTiO3/In2O3 photocatalytic composite fibers.
Sustainability 16 03988 g014
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Niu, J.; Hu, Q. Facile Fabrication of SrTiO3/In2O3 on Carbon Fibers via a Self-Assembly Strategy for Enhanced Photocatalytic Hydrogen Production. Sustainability 2024, 16, 3988. https://doi.org/10.3390/su16103988

AMA Style

Niu J, Hu Q. Facile Fabrication of SrTiO3/In2O3 on Carbon Fibers via a Self-Assembly Strategy for Enhanced Photocatalytic Hydrogen Production. Sustainability. 2024; 16(10):3988. https://doi.org/10.3390/su16103988

Chicago/Turabian Style

Niu, Jiantao, and Qi Hu. 2024. "Facile Fabrication of SrTiO3/In2O3 on Carbon Fibers via a Self-Assembly Strategy for Enhanced Photocatalytic Hydrogen Production" Sustainability 16, no. 10: 3988. https://doi.org/10.3390/su16103988

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop