Collection of Photocatalysts(202312)

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S-type Heterojunction of MOS2/g-C3N4: Construction and Photocatalysis
MA Rundong, GUO Xiong, SHI Kaixuan, AN Shengli, WANG Ruifen, GUO Ruihua
Journal of Inorganic Materials    2023, 38 (10): 1176-1182.   DOI: 10.15541/jim20230096
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Preparation of highly efficient and stable photocatalysts is crucial for the development of photocatalysis technology. In this study, the method of ultrasonic-assisted deposition and low-temperature calcination was used to prepare MoS2/g-C3N4 S-type heterojunction photocatalyst (MGCD). Effects of the phase structure, micro-morphology, optical absorption performance, X-ray photoelectron spectroscopy, electrochemical AC impedance, and photocurrent of the materials on the photocatalytic activity were comprehensively investigated. The results show that, after ultrasonic-assisted deposition-calcination treatment, MoS2 microspheres were broken, dispersed and combined on the surface of g-C3N4 nanosheets, and formed a kind of heterojunction. Under visible light, the degradation rate of 5%MGCD (with 5% MoS2 addition) for Rhodamine B (RhB) reached 99% in 20 min, and still reach 95.2% when the sample was reused for 5 times, showing good photocatalytic performance and stability. Further analysis from the point of view of the formation of built-in electric field shows that the band bending caused by built-in electric field, coupled with MoS2 and g-C3N4 in heterojunction, can effectively guide the directional migration of carriers, which can efficiently promote the separation of photogenerated carriers, thus improving the efficiency of photocatalytic reaction. Free radical capture experiment of heterojunction photocatalyst reveals that O2- and ·OH are the main active species in the catalytic degradation of RhB, followed by H+.

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Visible-light Catalytic Performance of ITO/TiO2 Nanotube Array Composite
WANG Mengtao, SUO Jun, FANG Dong, YI Jianhong, LIU Yichun, Olim RUZIMURADOV
Journal of Inorganic Materials    2023, 38 (11): 1292-1300.   DOI: 10.15541/jim20230178
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Photocatalysis has received extensive attention due to its advantages of mild reaction conditions and direct conversion of solar energy to chemical energy. Improving the solar absorption range and reducing the recombination of photo-generated “electron-hole” pairs are the hot topics in the field of photocatalysis. In this work, the amorphous TiO2 nanotube arrays (TiO2NTs) were prepared by anodic oxidation, and indium-tin (In-Sn) alloy was pressed into the amorphous TiO2NTs by a mechanical hydraulic method to make In9.45Sn1/TiO2NTs, then the In9.45Sn1/TiO2NTs were annealed in air to obtain indium tin oxide (ITO)/TiO2NTs. The photocatalytic properties of the obtained TiO2NTs, In9.45Sn1/TiO2NTs and ITO/TiO2NTs on the removal of methylene blue in aqueous solution were studied and compared. After 180 min visible light irradiation, the degradation efficiency of the ITO/TiO2NTs reaches 96.14%. The applying UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS) to explore the optical adsorption abilities of the samples shows the strongest absorbance of ITO/TiO2NTs. Combining the results of transient photocurrent responses, photocurrent density-potential, electrochemical impedance spectroscopy, and Mott-Schottky plots, the ITO/TiO2NTs have higher charge transfer capability and donor density than do other samples, which can reduce the recombination of holes and electrons, thus improving the visible-light catalytic performance. After five cycles, the degradation rate of the ITO/TiO2NTs still maintains 90.28%. Results of free radicals trapping experiments reveal that •O2- and •OH are the main active substances for the photocatalytic degradation.

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Synergy Effect of Pd Nanoparticles and Oxygen Vacancies for Enhancing TiO2 Photocatalytic CO2 Reduction
JIA Xin, LI Jinyu, DING Shihao, SHEN Qianqian, JIA Husheng, XUE Jinbo
Journal of Inorganic Materials    2023, 38 (11): 1301-1308.   DOI: 10.15541/jim20230170
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In this study, one-dimensional single-crystal TiO2 nanobelt arrays with surface oxygen vacancies were constructed by Pd-catalyzed oxygen reduction method in anoxic environment to address the problems of insufficient surface active sites and slow reaction kinetics of TiO2, low yield and poor selectivity of hydrocarbons in CO2 reduction products. The effects of surface oxygen vacancies and hydrogen spillover of Pd on the separation and transport of photogenerated carrier and the selectivity of reduction product were investigated from morphological structure, carrier behavior and photocatalytic performance. With high CO2 reduction activity of Pd-Ov-TNB, yields of CH4, C2H6 and C2H4 are 40.8, 32.09 and 3.09 µmol·g-1·h-1, respectively, and selectivity of hydrocarbons is as high as 84.52%, showing great potential in C-C coupling. Its excellent photocatalytic activity is attributed to the one-dimensional single-crystal nanobelt structure that increases the active specific surface area and crystallinity of the material, provides more active sites for the CO2 reduction and accelerates the segregated transport of photogenerated charges. Meanwhile, the oxygen vacancies enhance the surface accumulation of photogenerated charges, providing an electron-rich environment for CO2 reduction. In addition, Pd nanoparticles increase concentration of H* in the reaction system, and then transfer H* to active sites of CO2 adsorption on the catalyst surface through the hydrogen spillover effect, promoting the hydrogenation of reaction intermediates. Comprehensive advantages of Pd-nanoparticals contribute to the efficient conversion of CO2 to hydrocarbons.

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Construction and Photocatalytic Activity of Monoclinic Tungsten Oxide/Red Phosphorus Step-scheme Heterojunction
TUERHONG Munire, ZHAO Honggang, MA Yuhua, QI Xianhui, LI Yuchen, YAN Chenxiang, LI Jiawen, CHEN Ping
Journal of Inorganic Materials    2023, 38 (6): 701-707.   DOI: 10.15541/jim20220478
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S-scheme heterojunction has been extensively investigated for hydrogen evolution and environmental pollution issues. In this study, a monoclinic WO3/hydrothermally treated red phosphorus (HRP) S-scheme composite was prepared by hydrothermal method. XPS and EPR characterization confirmed that the monoclinic WO3/HRP composite formed S-scheme heterojunction. 5%WO3/HRP composite displayed the optimal photocatalytic activity under visible light irradiation, and its degradation rate of Rhodamine B (RhB) reached 97.6% after 4 min of visible light irradiation, while its hydrogen evolution rate reached 870.69 μmol·h-1·g-1 which was 3.62 times of that of pure HRP. This could be ascribed to the tight interfacial bonding between WO3 and HRP, and the formation of S-scheme heterostructure, enabling rapid separation of photogenerated carriers and therefore improving the strong redox capacity. This study provided a promising RP-based photocatalyst to meet the demand for clean energy and drinking water.

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Bi4O5Br2/CeO2 Composite with S-scheme Heterojunction: Construction and CO2 Reduction Performance
LI Yuejun, CAO Tieping, SUN Dawei
Journal of Inorganic Materials    2023, 38 (8): 963-970.   DOI: 10.15541/jim20230003
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One of the basic challenges of CO2 photoreduction is to develop efficient photocatalysts. As an effective strategy, constructing heterostructure photocatalysts with intimate interfaces can enhance interfacial charge transfer for realizing high photocatalytic activity. Herein, a novel photocatalytic material, Bi4O5Br2/CeO2 composite fiber (B@C-x, x refers to the amount of reactant), was constructed by embeding CeO2 nanofibers on Bi4O5Br2 nanosheets via an electrospinning combined with hydrothermal method. Its composition, morphology and photoelectric properties were characterized. The results show that Bi4O5Br2/CeO2 heterojunction with appropriate Bi4O5Br2 content can significantly improve the photocatalytic performance of CeO2 nanofibers. Compared with pure Bi4O5Br2 and CeO2, B@C-2 exhibited the best photocatalytic activity under simulated sunlight. The Bi4O5Br2/CeO2 exhibited improved photocatalytic CO2 reduction performance with a CO generation rate of 8.26 μmol·h−1·g−1 without using any sacrificial agents or noble co-catalysts. This can be attributed to the tight interfacial bonding between Bi4O5Br2 and CeO2 and the formation of S-scheme heterojunction, which enables the efficient spatial separation and transfer of photogenerated carriers. This work provides a simple and efficient method for directional synthesis of Bi-based photocatalytic composites with S-scheme heterojunction and illustrates an applicable tactic to develop potent photocatalysts for clean energy conversion.

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Preparation of TiHAP@g-C3N4 Heterojunction and Photocatalytic Degradation of Methyl Orange
WU Lin, HU Minglei, WANG Liping, HUANG Shaomeng, ZHOU Xiangyuan
Journal of Inorganic Materials    2023, 38 (5): 503-510.   DOI: 10.15541/jim20220413
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A composite photocatalyst (TiHAP@g-C3N4) consisting of Ti doped hydroxyapatite and g-C3N4 was synthesized through hydrothermal route. Its structure and optical property were characterized by various means and photocatalytic activity was evaluated through methyl orange (MO) degradation experiments. Results show that short rod-shaped TiHAP in the sample grows on the surface of g-C3N4. Both TiHAP and g-C3N4 maintain their original crystal shape and chemical structure. As-prepared TiHAP@g-C3N4 is of high purity with specific surface area of 107.92 m2/g, which is increased about 135% and 44% as compared with sole TiHAP and sole g-C3N4, respectively. The highest MO degradation rate of 96.35% is achieved within 120 min by TiHAP@g-C3N4 at the concentration of 1.0 g/L and pH 7. More than 80.02% of MO was removed in every of three cyclic tests, demonstrating good and stable photocatalytic performance of TiHAP@g-C3N4. Holes (h+) play the largest role in the MO degradation process, followed by ·O2- and ·OH. The constructed TiHAP@g-C3N4 heterojunction enhances light absorption, improves separation efficiency of photoelectrons-h+, and preserves more redox-prone TiHAP valence band h+ and g-C3N4 conduction band electrons. Therefore, as-synthesized TiHAP@g-C3N4 can be a promising catalyst in photocatalytic degradation.

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BiOBr/ZnMoO4 Step-scheme Heterojunction: Construction and Photocatalytic Degradation Properties
MA Xinquan, LI Xibao, CHEN Zhi, FENG Zhijun, HUANG Juntong
Journal of Inorganic Materials    2023, 38 (1): 62-70.   DOI: 10.15541/jim20220192
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Photocatalysis is widely used for the removal of refractory organic pollutants in water, but the catalytic activity of semiconductor photocatalysts is significantly inhibited due to the high recombination rate of photogenerated electrons and holes. In this study, an S-scheme BiOBr/ZnMoO4 composite was successfully prepared by a facile solvothermal method. The structure analysis, in-situ XPS, work function test, free radical capture and ESR experiment confirmed that the BiOBr/ZnMoO4 composite formed an S-scheme heterojunction. The experimental results show that BiOBr/ZnMoO4 heterojunction with appropriate ZnMoO4 content can significantly improve the photocatalytic performance of BiOBr. Compared with pure BiOBr and ZnMoO4, 15% BiOBr/ZnMoO4 exhibits the best photocatalytic activity under visible light irradiation, and the photocatalytic degradation rate of bisphenol A reaches 85.3% (90 min). The rate constants of photodegradation of ciprofloxacin are 2.6 times that of BiOBr and 484 times that of ZnMoO4, respectively. This can be attributed to the tight interfacial bonding between BiOBr and ZnMoO4 and the formation of S-scheme heterojunction, which enables the efficient spatial separation and transfer of photogenerated carriers. This work provides a simple and efficient method for the directional synthesis of Bi-based S-scheme heterojunction photocatalytic materials, and provides a new theory and experimental basis for further understanding of the structure-activity relationship of Bi-based multi-heterojunction photocatalytic materials.

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Two-dimensional g-C3N4 Compositing with Ag-TiO2 as Deactivation Resistant Photocatalyst for Degradation of Gaseous Acetaldehyde
XUE Hongyun, WANG Congyu, MAHMOOD Asad, YU Jiajun, WANG Yan, XIE Xiaofeng, SUN Jing
Journal of Inorganic Materials    2022, 37 (8): 865-872.   DOI: 10.15541/jim20220123
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The photocatalysts deactivation is one of the major issues, which lowers the usefulness of photocatalytic oxidation technology for the removal of low content volatile organic compounds (VOCs). Here, we carried out a series of experiments to demonstrate that the photocatalysts stability could be significantly improved via coupling the oxide base semiconductors, i.e., TiO2 with 2D materials such as graphitic carbon nitride (g-C3N4). Initially, when Ag modified TiO2 (AT) was used for the gaseous acetaldehyde degradation, a robust deactivation was observed within 60 min. The AT catalyst completely lost its activity when the reaction time was extended to 400 min. On the contrary, the g-C3N4 modified AT (CAT) showed superior photocatalytic performance and improved stability (600 min). The in-situ FT-IR, PL, and photocurrent studies suggested that the accumulation of reaction intermediates in the case of AT fundamentally caused the deactivation. However, the g-C3N4 provided excessive adsorption sites for the reaction by-products which improved the stability. Additionally, the PL and ESR studies suggested that the existence of g-C3N4 improved the charge separation and production of reactive oxygen species, which facilitated the photodegradation of acetaldehyde and ultimate reaction products. This study realizes the usefulness of 2D materials for developing stable and visible light active photocatalysts for applications in sustainable VOC abatement technology.

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Preparation and Properties of Ag@C3N4 Photocatalyst Supported by Hydrogel
WANG Xiaojun, XU Wen, LIU Runlu, PAN Hui, ZHU Shenmin
Journal of Inorganic Materials    2022, 37 (7): 731-740.   DOI: 10.15541/jim20210535
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Graphitic carbon nitride (g-C3N4) is widely used in the field of photocatalysis due to its unique two-dimensional planar structure and suitable energy band structure. However, it has some disadvantages such as fast recombination of the electron-hole, low visible-light utilization efficiency and poor dispersion in water, which hinder its application. In this study, the hydrogel prepared by sodium alginate was used as matrix to improve the dispersion of Ag@C3N4 composite in water, and at the same time enhanced the separation efficiency of photoelectron-holes pairs, thus improving its photocatalytic performance. Firstly, g-C3N4 was synthesized by thermal polymerization and then exfoliated into nanosheets by ultrasound. Then, Ag nanoparticles were deposited in situ on the surface of g-C3N4 by solution method to prepare Ag@C3N4. Finally, hydrogel loaded with Ag@C3N4 (SA/Ag@C3N4) was obtained by using calcium ion as crosslinker and sodium alginate (SA) as precursor. The morphology, microstructure and phase composition of the as-prepared photocatalyst were characterized. The as-prepared SA/Ag@C3N4 exhibited a 1.5 times higher photocatalytic degradation rate of methyl orange than that of Ag@C3N4. The catalytic mechanism was investigated by photoluminescence spectrum, time resolved photoluminescence spectrum and electron paramagnetic resonance spectrum. The results showed that the surface plasmon resonance effect of silver nanoparticles together with the porous structure and mass transfer channel of sodium alginate hydrogel plays a synergistic role in the enhancement of photocatalytic performance.

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Preparation of SiO2@Ag@SiO2@TiO2 Core-shell Structure and Its Photocatalytic Degradation Property
CHI Congcong, QU Panpan, REN Chaonan, XU Xin, BAI Feifei, ZHANG Danjie
Journal of Inorganic Materials    2022, 37 (7): 750-756.   DOI: 10.15541/jim20210685
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Photocatalytic degradation is an eco-friendly and high-efficiency way to degrade dye pollutants which has broad application prospects in water pollution control. In this study, the multi-layer core-shell structure of SiO2@Ag@SiO2@TiO2 was synthesized by different methods as a photocatalyst for pollutant degradation, with oxidation-reduction method, modified Stöber method and hydrothermal method in turn. Effect of silver nitrate (AgNO3), tetraethyl orthosilicate (TEOS) and tetrabutyl titanate (TBOT) on the coating effect were discussed. Microstructure, phase structure, pore structure parameters and photoelectrical properties of SiO2-based multi-layer core-shell structure were systematically analyzed by various characterization methods while its degradation performance of methylene blue (MB) was also studied and discussed. The results show that when the mass ratio of AgNO3, TEOS and TBOT to SiO2 is 5 : 2.4 : 6 : 1, each layer of the multi-layer cored shell structure achieves the optimal coating effect. Compared with SiO2@TiO2 and SiO2@Ag@TiO2, the core-shell structure of SiO2@Ag@SiO2@TiO2 photocatalyst has the best photocatalytic activity. Its photocatalytic degradation efficiency is close to 93% after simulated visible light irradiation for 45 min, and degradation efficiency keeps at 90% after 4 cycles of recycling tests.

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