RARE METALS
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2025
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IF 11
Chen Taoran,Qin Tian,Sun Hongli,Su Chenliang
Photocatalytic oxidation of toluene to valuable benzaldehyde offers a promising pathway for sustainable production of fine chemicals and pharmaceuticals. In this process, photogenerated holes play a crucial role in C(sp 3 )-H bond dissociation. However, the photocatalytic performance of current photocatalysts is often hindered by the low separation and transfer efficiency of photogenerated charges. In this work, we presented a perovskite-based heterostructure via in situ growth of defective WO 3- x nanosheets on Cs 2 AgBiBr 6 nanoparticles for photocatalytic toluene transformation. In situ Fourier transform infrared spectroscopy tests proved the introduction of oxygen-deficient WO 3- x component enhanced the chemisorption of molecular oxygen. The in situ electron paramagnetic resonance and 4-chloro-7-nitro-1,2,3-benzoxadiazole fluorescence measurements further confirmed the presence of oxygen vacancies, and the formation of heterostructure synergistically accelerated the formation of the superoxide radicals and the transfer of photogenerated charge carriers. Under visible light irradiation, Cs 2 AgBiBr 6 /WO 3- x photocatalyst could effectively oxidize toluene toward benzaldehyde with a conversion rate of 9020 μmol g −1 h −1 , which was a 3.5-fold increase over that of the unmodified Cs 2 AgBiBr 6 . Graphical abstract
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
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2026
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IF 5.4
Yingying Qian,Jianhai Wang,Yuesong Shen
Heterojunction engineering has garnered significant attention in photocatalysis as an effective strategy to address the rapid carrier recombination dynamics in semiconductor photocatalysts. The core challenge in constructing high-performance heterojunction systems lies in establishing optimized interfacial connections to achieve directional charge carrier migration. This study proposed a temperature-regulated band engineering strategy, through precise control of Ni-MOFs growth temperature and integration with WO 3-x possessing exceptional photothermal conversion capacity, to successfully construct an efficient Z-scheme heterojunction system. When the synthesis temperature of the Ni-MOF reached 140 °C, its conduction band negatively shifted to −1.2 eV (vs. NHE), resulting in a well-matched Z-scheme heterojunction with WO 3-x . The optimized 140-Ni-MOF/WO 3-x heterojunction demonstrated remarkable enhancement in charge separation efficiency while preserving strong redox capabilities through the Z-scheme charge transfer pathway. Under mild gas-solid reaction conditions (H 2 O as electron donor), the optimized catalyst exhibited excellent CO 2 reduction performance, achieving a CO production rate of 111.17 μmol·g −1 with 96.92 % selectivity. The temperature-depended modulation strategy for MOF electronic band structure proposed in this study paved the way for constructing efficient MOF-based photocatalysts.
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JOURNAL OF ALLOYS AND COMPOUNDS
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2026
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IF 6.7
Chenlong Zhao,Hao Zhang,Yaoyang Wang,Lihailiang Xu,Yuan Wan,Xianwu Xiu
Noble metal and semiconductor composite substrates possess high sensitivity, excellent stability, and selective enhancement, establishing them as a significant research focus in the field of surface-enhanced Raman scattering (SERS). Tungsten oxide (WO 3 ), as an n-type semiconductor with high thermal stability, corrosion resistance, and outstanding electrochromic properties, has great potential in SERS research. This study designed and fabricated a flexible composite SERS substrate based on oxygen-deficient tungsten oxide nanostructures, achieving optimal detection performance by combining 3D WO 3-x nanowires on carbon cloth (CC) with silver nanoparticles (AgNPs). The high-aspect-ratio WO 3-x nanowires were prepared using a functional group-induced "competitive growth" hydrothermal method. The bandgap was modulated through atmosphere annealing to introduce oxygen vacancies (self-doping), which effectively improved the charge transfer efficiency and surface plasmon resonance, thereby achieving superior SERS performance. This composite SERS substrate benefits from the synergistic contributions of electromagnetic and chemical enhancement mechanisms, achieving ultra-low detection limits of 10 −12 M for Rhodamine 6 G (R6G). Within the concentration range of 10 −7 M to 10 −12 M, there is a good linear relationship between concentration and peak intensity, demonstrating excellent quantitative analysis capabilities. Furthermore, leveraging its mechanical flexibility, this substrate holds broad application prospects in areas such as food safety and environmental monitoring.
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ACS Applied Nano Materials
·
2023
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IF 5.9
Zhiming Sun,Yuhang Gao,Chaogang Ban,Jiazhi Meng,Jinshu Wang,Kaiwen Wang,Liyong Gan
Oxygen vacancy (Vo) engineering is a powerful tool to improve semiconductor metal oxide-based surface-enhanced Raman scattering (SERS) activity due to the enriched surface states of substrates. However, the current energy-consuming high-temperature hydrogen reduction methods of introducing Vo and the poor sensitivity impede practical applications of semiconductor SERS. In this work, a facile solvothermal method was developed to prepare ultrafine WO3–x nanorods (∼3 nm width) for high-performance SERS substrates. The lowest detection limit of the rhodamine 6G (R6G) molecule on the Vo substrate can be as low as 10–10 mol/L and exceeds that of unmodified WO3 by more than two orders of magnitude. Experimental and calculated results suggest that the Vo-induced localized surface plasmon resonance (LSPR), diverse vibronic coupling, and enhanced charge transfer synergistically account for this outstanding activity. These findings can provide insights into the rational design of oxygen vacancy-tailored semiconductor SERS substrates.
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SEPARATION AND PURIFICATION TECHNOLOGY
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2022
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IF 9.136
Ling Cheng,Xianglong Yang,Xiaomei Chen,Chunling Lv,Jin Mao,Qi Zhang,Peiwu Li
A surface oxygen vacancy-engineered WO 3-x film with enhanced photoelectrocatalytic (PEC) activity for the detoxification of deoxynivalenol (DON) was successfully synthesized via an improved sol-gel method. The presence of oxygen vacancy was verified by high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, Raman spectra and electron spin resonance spectroscopy. The introduction of oxygen vacancy into WO 3-x film substantially enhanced its absorption in visible region, and facilitated its transfer and separation of photogenerated charges. This made the WO 3-x film to have excellent PEC activity for the detoxification of DON under visible light illumination at a low bias of +0.3 V. The percentage of DON removed was up to 86.4 % after being treated with PEC for 2 h. When the bias potential applied was further increased, there were no obvious changes in the degradation efficiency of the film. The cell viabilities were dramatically enhanced with prolonged time, which were over 95 % after 2 h PEC treatment compared to the control. Through the analysis of eight intermediates that were separated and identified by high performance liquid chromatography-mass spectrometry, it can be concluded that the reduction of DON and the cleavage of double bond at C9 C10, epoxy group at C12 13 and hydroxyl group at C3 in DON could greatly reduce the toxicity, and the detoxification mechanism of this PEC system was proposed. This work can provide further insights into DON detoxification using PEC system with low bias.
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Nanomaterials
·
2022
·Vol. 12
·期 10
·1637
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IF 5.719
Siqi Qu,Jing Guan,Dongqi Cai,Qianshuo Wang,Xiuyun Wang,Wei Song,Wei Ji
Electrochemical surface-enhanced Raman scattering (EC-SERS) spectroscopy is an ultrasensitive spectro-electrochemistry technique that provides mechanistic and dynamic information on electrochemical interfaces at the molecular level. However, the plasmon-mediated photocatalysis hinders the intrinsic electrochemical behavior of molecules at electrochemical interfaces. This work aimed to develop a facile method for constructing a reliable EC-SERS substrate that can be used to study the molecular dynamics at electrochemical interfaces. Herein, a novel Ag-WO3−xelectrochromic heterostructure was synthesized for EC-SERS. Especially, the use of electrochromic WO3−xfilm suppresses the influence of hot-electrons-induced catalysis while offering a reliable SERS effect. Based on this finding, the real electrochemical behavior of p-aminothiophenol (PATP) on Ag nanoparticles (NPs) surface was revealed for the first time. We are confident that metal-semiconductor electrochromic heterostructures could be developed into reliable substrates for EC-SERS analysis. Furthermore, the results obtained in this work provide new insights not only into the chemical mechanism of SERS, but also into the hot-electron transfer mechanism in metal-semiconductor heterostructures.Keywords:SERS;defect states;EC-SERS;Ag-WO3−xfilm
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
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2024
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IF 4.3
Qinli Ye,Miaomiao Wu,Qian Xu,Shuwen Zeng,Tao Jiang,Wei Xiong,Songyin Fu,Muhammad Danang Birowosuto,Chenjie Gu
The Surface-enhanced Raman scattering (SERS) is an attractive optical detecting method with high sensitivity and detectivity, however challenges on large-area signal uniformity and complex spectra analysis methods always retards its wide application. Herein, a highly sensitive and uniform SERS detection strategy supported by porous carbon film/WO 3-x nanosheets (PorC/WO 3-x ) based noble-metal-free SERS substrate and deep learning algorithm are reported. Experimentally, the PorC/WO 3-x substrate was prepared by high-temperature annealing the PorC/WO 3 films under the argon atmosphere. The defect density of the WO 3 was controlled by tuning the reducing reaction time during the annealing process. The SERS performance was evaluated by using R6G as the Raman reporter, it showed that the SERS intensity obtained on the substrate with the optimal annealing time of 3 h was about 8 times as high as that obtained on the PorC/WO 3 substrate without annealing treatment. And detection limit of 10 -7 M and Raman enhancement factor of 10 6 could be achieved. Moreover, the above optimal SERS substrate was utilized to detect flavonoids of quercetin, 3-hydroxyflavone and flavone, and a deep learning algorithms was incorporated to identify the quercetin. It revealed that quercetin can be accurately detected within the above flavonoids, and lowest detectable concentration of 10 -5 M can be achieved.
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Surfaces and Interfaces
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2018
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IF 0
Kainan Song,Xueming Liu,Chen Tian,Hong Deng,Jide Wang,Xintai Su
In present study, two group of WO 3-x nanocrystals (NCs) have been prepared via a facile solvothermal process and their photocatalytic activities for dehydration of isopropyl alcohol (IPA) to propylene (C 3 H 6 ) under visible light irradiation have been studied. The photocatalysts are characterized by XRD , FSEM, HRTEM , XPS and UV–vis spectroscopic study. As for WO 3-x NCs synthesized under different temperature, the highest photocatalytic efficiency was achieved for the W 18 O 49 NCs prepared at 160 °C at C 3 H 6 evolution rate of 145 μmol h −1 g −1 . When it comes to the WO 3-x NCs obtained using different solvents, the sea urchin-like W 18 O 49 microspheres synthesized in ethanol has the greatest activity for photocatalytic dehydration of IPA. Their outstanding photocatalytic performances may stem from the large amount of oxygen vacancies (OVs) on their surfaces. The above results suggest the high potential of WO 3-x NCs in application for C 3 H 6 production.
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JOURNAL OF ALLOYS AND COMPOUNDS
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2019
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IF 4.175
Yunfang Huang,Hui Xu,Dan Luo,Yuezhu Zhao,Yu Fang,Qiyao Guo,Yuelin Wei,Leqing Fan,Jihuai Wu
To improve the utilization efficiency of solar energy and separation of photogenerated carries, a novel three-dimensional (3D) WO 3-x /Bi/BiOCl hierarchical heterostructures with broad spectrum responsive photocatalytic activity have been fabricated through a facile solvothermal technique. The influences of varying loading of WO 3-x on the physical performances of the as-obtained composites were systematically characterized by X-ray diffraction, scanning electron microscope, transmission electron microscopy , X-ray photoelectron spectroscopy, optical absorbance, photoluminescence and specific surface areas. The WO 3-x /Bi/BiOCl displayed a strong optical absorption from 250 to 2500 nm, and showed the superior photocatalytic performance in degradation of rhodamine B (RhB) than that of individual components. Among the as-prepared samples, the sample S24 with the appropriate content of WO 3-x displayed the best photocatalytic performance, which can photodegrade RhB with the efficiency of 100%, 100% and 96% under the UV light within 8 min, visible light within 3 min and near-infrared light within 120 min exposure, respectively. Furthermore, a plausible mechanism of the RhB degradation on WO 3-x /Bi/BiOCl photocatalysts under the near-infrared light irradiation was proposed according to the photocatalytic activity and radical species trapping experiments.
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Molecular Catalysis
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2026
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IF 4.3
Kai-Xiong Dai,Kuan Wang,Yu-Rui Chao,Yue Yang,Xin-Peng Li,Zhen-Hong He,Weitao Wang,Huan Wang,Zhao-Tie Liu
The photothermal selective oxidation of cyclohexane to produce KA oil (cyclohexanone and cyclohexanol) under solvent-free conditions holds significant importance. However, the one-step photothermal oxidation of cyclohexane to produce downstream high-value products adipic acid (AA) remains a challenge at present. Hereby, a highly efficient Z-scheme CeCoO 3 /WO 3-x heterojunction photothermal catalyst was designed and constructed based on the interface engineering. Through photothermal synergistic effects, CeCoO 3 /WO 3-x achieves the efficient and highly selective oxidation of cyclohexane under solvent-free conditions and visible-light irradiation. Notably, the cyclohexane conversion reached 13.7 % with an overall selectivity of 97.6 % (where liquid KA oil selectivity was 65.2 % and solid AA selectivity was 32.4 %). The enhanced catalytic performance stems from the Z-scheme heterojunction structure, which effectively promotes photogenerated charge separation and transport, suppresses charge recombination, broadens the light response range, and exhibits a large specific surface area with porous structure. This study provides novel insights for designing highly efficient photothermal catalytic systems for the selective oxidation of low-carbon alkanes.
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NANOTECHNOLOGY
·
2025
·Vol. 36
·期 45
·455703
·
IF 2.8
Shuangqi Dong,Yuge Feng,Chao Wang,Zhaopeng Huang,Ajit Khosla,Hui Zhang
As a transition-metal oxide semiconductor with variable tungsten valence states and abundant oxygen vacancies, WO3−x has attracted broad interest because its localized surface plasmon resonance performance can be tuned via controlling the concentration of oxygen vacancies. In this work, Cs-doped WO3−x nanosheets (Cs-WO3−x) were synthesized by solvothermal method. Subsequently, Cs-WO3−x were further annealed in hydrogen and air atmosphere, respectively, forming a compact, highly crystalline surface layer (with thickness of ∼14 nm) on the surface while retaining abundant oxygen vacancy defects in the center region (denoted as a-Cs-WO3−x). As a proof-of-concept, the as-prepared nanosheets were employed as light harvesting materials in photocatalytic degradation of methyl orange (MO), a-Cs-WO3−x nanosheets demonstrate significantly improved degradation efficiency with respect to WO3−x and Cs-WO3−x counterparts. The enhanced performance can be attributed to the hot-carrier transfer routes, which relies on not only direct electron transfer but also the more efficient plasmon-induced resonant energy transfer pathway. This work develops new pathway and provides important insights into the regulation of oxygen vacancies.
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APPLIED SURFACE SCIENCE
·
2022
·
IF 7.392
Wei Ding,Xingjian Wang,Chao Yang,Pengzhen Wang,Weiliang Tian,Kun Zhao,Kewei Zhang
Interfacial composite with improved carrier separation is promising to achieve multifunctionality and thus contribute to the carbon neutrality and sustainability of our society. Herein, we demonstrate a facile defect-assisted photo-reduction strategy to rationally design interfacial rGO/WO 3−x composites with versatile properties. Under light irradiation, the accumulated electrons in oxygen-defective WO 3−x endow partial restoration of the π network within GO nanosheets. The in-situ formed rGO/WO 3−x not only broadens optical absorption but also accelerates carrier migration, enabling superior gas-sensing, photocatalytic and energy storage applications. When used as sensing material of smart sensors, the resultant rGO/WO 3−x exhibits high response (8.4), low detection limit (92 ppb), good selectivity, fast response, and long-term stability (7 weeks) to ppm-level triethylamine. As an efficient photocatalyst, the photocatalytic kinetic of rGO/WO 3−x towards visible-light-driven RhB degradation is promoted about 7 times as compared with that of pristine WO 3−x . The synergism of suitable components endows the rGO/WO 3−x supercapacitor with high capacity (380F/g) over prolonged cycling. This work provided a successful approach for in-situ formation of interfacial composites and thus broadens the material’s versatility for advanced nanotechnology.
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