Journal Article10.1038/s41467-024-49005-6
Photocatalytic toluene oxidation with nickel-mediated cascaded active units over Ni/Bi2WO6 monolayers
Yingzhang Shi,Yingzhang Shi,Yingzhang Shi,Yingzhang Shi,Yingzhang Shi,Yingzhang Shi,Yingzhang Shi,Yingzhang Shi,Yingzhang Shi,Yingzhang Shi,Yingzhang Shi +10 more
TL;DR: Photocatalytic toluene oxidation with nickel-mediated cascaded active units over Ni/Bi2WO6 monolayers efficiently converts toluene into benzaldehyde through the design of cascaded active units consisting of unsaturated W atoms and Bi/O frustrated Lewis pairs.
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Abstract: Abstract Adsorption and activation of C–H bonds by photocatalysts are crucial for the efficient conversion of C–H bonds to produce high-value chemicals. Nevertheless, the delivery of surface-active oxygen species for C–H bond oxygenation inevitably needs to overcome obstacles due to the separated active centers, which suppresses the catalytic efficiency. Herein, Ni dopants are introduced into a monolayer Bi 2 WO 6 to create cascaded active units consisting of unsaturated W atoms and Bi/O frustrated Lewis pairs. Experimental characterizations and density functional theory calculations reveal that these special sites can establish an efficient and controllable C–H bond oxidation process. The activated oxygen species on unsaturated W are readily transferred to the Bi/O sites for C–H bond oxygenation. The catalyst with a Ni mass fraction of 1.8% exhibits excellent toluene conversion rates and high selectivity towards benzaldehyde. This study presents a fascinating strategy for toluene oxidation through the design of efficient cascaded active units.
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Figures
Fig. 4 | Photocatalytic performance for toluene oxidation. The photocatalytic oxidation of TL over different photocatalyst (a), The time-dependent process of the oxidation of TL over 1.8Ni/BWO (b) and BWO (c), error bars are mean ± SD based on three repeat experiments. 
Fig. 5 | The adsorption behavior of toluene and O2, and the reaction process analysis. Time-dependent in situ DRIFT spectra of 1.8 Ni/BWO (a) and BWO (b) in the dark under O2 atmosphere. O2-TPD spectra of the prepared samples (c). Timedependent in situ DRIFT spectra of 1.8 Ni/BWO in the dark under toluene and O2 atmosphere (d). Time-dependent in situ DRIFT spectra of 1.8 Ni/BWO (e) and BWO (g) in a toluene and O2 atmosphere under visible light irradiation. Mass spectra of BD produced in 16O2 and 18O2 atmosphere over 1.8 Ni/BWO (f). 
Fig. 1 | Synthesis diagramandcrystalphase structure andmorphology analysis. a Schematic diagram for the synthesis of Ni/BWO, XRDpatterns, 2θ from25° to 35° (b), FT-IR spectra (c), and Raman spectra (d) of the samples. AFM image (e), TEM (f), and HRTEM (g) image of 1.8 Ni/BWO. 
Fig. 6 | DFT calculations of the C-H activation and oxygen transfer pathway, and possible mechanism. The activation and delivery of O2 with the calculated energy profiles on the optimized structural models of Ni/BWO-(001) (a). Calculated energy profiles of toluene adsorbed on different structure models (b), corresponding geometries and energies of TS1, TS2, TS3, and TS4 (c), Transient charge density difference image of toluene adsorbed on the FLPs of Ni/BWO-(001) (d), The possible mechanism for photocatalytic oxidation of toluene on 1.8 Ni/ 
Fig. 2 | Atomic scale composition and structure analysis. HAADF image (a) and the corresponding EDS maps (b–e) of 1.8 Ni/BWO sample. The atomic-resolution iDPC image is displayed in (f), where the enlarged region from the white box shows the vacancy of O ion (highlighted by red circles) and the substitution ofWbyNi (g). The line profiles of O (h) andW (i) signals are extracted from thewhite boxes in (g). 
Fig. 3 | The characterization and DFT calculations of CAUs. XPS spectra of W4f (a) and Bi 4f (b), EPR spectra (c) of the prepared samples. W L3-edge XAFS spectra: k3-weighted Fourier transform EXAFS spectra (d). The optimized structure model of Ni/BWO (010) and (001) with the charge density difference (e). The formation energy (Ef) ofOV (f). Top view of the optimized configurations ofNi/BWO (010): (g) initial state and (h) final state of forming OV; Ni/BWO (001): (i) initial state and (j) final state of forming OV and FLPs.
Citations
Ultrathin 2D/2D MoS2/Bi2WO6 S-scheme heterojunction for boosting photocatalytic degradation of ciprofloxacin
Qilai Chen,Cheng Liu,Rui Liu,Yidong Hou,Jinhong Bi,Jimmy C. Yu,Ling Wu +6 more
7
Enabling Interfacial Lattice Matching by Selective Epitaxial Growth of CuS Crystals on Bi2WO6 Nanosheets for Efficient CO2 Photoreduction into Solar Fuels
Jiaqi Tian,Yangyang Zhang,Zuhao Shi,Zhongyi Liu,Zaiwang Zhao,Jing Wang,Neng Li,Hongwei Huang +7 more
TL;DR: Researchers developed a 2D/2D p-n heterojunction CuS-Bi2WO6 photocatalyst via hydrothermal synthesis, enabling efficient CO2 reduction into solar fuels with high CO and CH4 yields, outperforming individual components and physical mixtures.
7
Observation on Switching Properties of WO<sub>3</sub>-Based H<sub>2</sub> Sensor Regulated by Temperature and Gas Concentration
Beixi An,Yifan Yang,Yanrong Wang,Ruixia Li,Zhengkun Wu,Peizhe Wang,Tingyu Zhang,Ruiqi Han,Erqing Xie +8 more
TL;DR: This study investigates the switching properties of WO3-based H2 sensors, exploring the effects of temperature and gas concentration on their performance, with implications for their potential application in hydrogen detection and sensing technologies.
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Grafting anthraquinone on ultrathin C3N4 for selective toluene photooxidation
Xiong Wang,Guang‐Hui Chen,Li Yang,Tian Sheng,Binghao Wang,Biao Hu,Xing-Sheng Hu,Chao Peng,Lang Chen,Shuang‐Feng Yin +9 more
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Bi<sub>3</sub>TiNbO<sub>9</sub>/Bi<sub>2</sub>S<sub>3</sub> Heterojunction for Efficient Photosynthesis of H<sub>2</sub>O<sub>2</sub> in Pure Water
Yuan Teng,Ling‐Ling Ning,Chao‐Wen Tan,Jing Zhao,Y. H. Xiong,Hong‐Lin Zou,Zi‐Ming Ye,Xueming Zhang,Dai‐Bin Kuang,Youji Li +9 more
TL;DR: Researchers develop a 2D/1D Bi3TiNbO9/Bi2S3 heterojunction via in situ vulcanization, achieving a 810 µmol g−1 h−1 H2O2 yield rate, 6.18-18.0 times higher than pristine materials, with unprecedented stability and efficiency in artificial photosynthesis.
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