Pub Date : 2024-12-26DOI: 10.1016/j.jphotochem.2024.116246
Michael S. Elioff , Jingqiu Hu
A novel acridinium-anilide-bithiophene triad (1) was synthesized and the intramolecular photoinduced electron transfer (PET) in the triad was investigated in various media. In the triad, the acridinium (Ac) is the electron acceptor and the chromophore. The bithiophene and anilide are electron donors. The lifetimes of the charge-shift state (CSH) emission varied from picoseconds in organic solvents to the nanosecond time domain in solid matrix. Long-lived charge separation transient species in the 200-microsecond time domain were observed in a solid glass matrix based on laser flash photolysis experiments. Polymeric media and solid glass matrices were observed to significantly slow the back-electron transfer of the CSH, resulting in stronger CSH emission and longer lifetimes.
{"title":"A molecular wire: Electron transfer in an acridinium-based triad in various media","authors":"Michael S. Elioff , Jingqiu Hu","doi":"10.1016/j.jphotochem.2024.116246","DOIUrl":"10.1016/j.jphotochem.2024.116246","url":null,"abstract":"<div><div>A novel acridinium-anilide-bithiophene triad (<strong>1</strong>) was synthesized and the intramolecular photoinduced electron transfer (PET) in the triad was investigated in various media. In the triad, the acridinium (Ac) is the electron acceptor and the chromophore. The bithiophene and anilide are electron donors. The lifetimes of the charge-shift state (CSH) emission varied from picoseconds in organic solvents to the nanosecond time domain in solid matrix. Long-lived charge separation transient species in the 200-microsecond time domain were observed in a solid glass matrix based on laser flash photolysis experiments. Polymeric media and solid glass matrices were observed to significantly slow the back-electron transfer of the CSH, resulting in stronger CSH emission and longer lifetimes.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"462 ","pages":"Article 116246"},"PeriodicalIF":4.1,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143166538","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The study successfully doped vanadium into the WO3 lattice to enhance its activity for the effective photocatalytic degradation of tetracycline, a pollutant known to induce various adverse effects on environmental and ecological systems due to its excessive use and discharge. The results demonstrated that vanadium doping effectively reduced band gap energy and enhanced electron-hole separation efficiency of WO3. Under visible light, V-WO3 generated a large number of electron-hole pairs for tetracycline degradation. The study further revealed that the optimal vanadium doping content to maximize the degradation efficiency of WO3 was 3 wt% (V/W). Exceeding this doping content led to the formation of V2O5 on the WO3 surface. The V2O5 occupied active sites and/or acted as centers for the recombination of generated electron-hole pairs, thereby reducing the photocatalytic performance of WO3. Additionally, the study identified that the optimal pH for tetracycline degradation using 3 V-WO3 was 6. The 3 V-WO3 demonstrated high photocatalytic efficiency, achieving complete mineralization of tetracycline. Finally, the study confirmed that 3 V-WO3 exhibited excellent stability during photocatalysis and could be effectively recovered after use.
{"title":"Optimization of photocatalysis using vanadium doped WO3 under visible light to completely eliminate residual antibiotics in aqueous environment","authors":"Thanh-Dong Pham , Nguyen Thi Hanh , Nguyen Viet Khoa , Nguyen Van Noi , Nguyen Thi Dieu Cam , Ha Minh Ngoc , Phuong Thao , Hoang Thu Trang , Nguyen Thuy Huong","doi":"10.1016/j.jphotochem.2024.116243","DOIUrl":"10.1016/j.jphotochem.2024.116243","url":null,"abstract":"<div><div>The study successfully doped vanadium into the WO<sub>3</sub> lattice to enhance its activity for the effective photocatalytic degradation of tetracycline, a pollutant known to induce various adverse effects on environmental and ecological systems due to its excessive use and discharge. The results demonstrated that vanadium doping effectively reduced band gap energy and enhanced electron-hole separation efficiency of WO<sub>3</sub>. Under visible light, V-WO<sub>3</sub> generated a large number of electron-hole pairs for tetracycline degradation. The study further revealed that the optimal vanadium doping content to maximize the degradation efficiency of WO<sub>3</sub> was 3 wt% (V/W). Exceeding this doping content led to the formation of V<sub>2</sub>O<sub>5</sub> on the WO<sub>3</sub> surface. The V<sub>2</sub>O<sub>5</sub> occupied active sites and/or acted as centers for the recombination of generated electron-hole pairs, thereby reducing the photocatalytic performance of WO<sub>3</sub>. Additionally, the study identified that the optimal pH for tetracycline degradation using 3 V-WO<sub>3</sub> was 6. The 3 V-WO<sub>3</sub> demonstrated high photocatalytic efficiency, achieving complete mineralization of tetracycline. Finally, the study confirmed that 3 V-WO<sub>3</sub> exhibited excellent stability during photocatalysis and could be effectively recovered after use.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"462 ","pages":"Article 116243"},"PeriodicalIF":4.1,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143166619","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Efficient materials are needed to address water contamination by pharmaceuticals, a growing environmental concern. Sulfamethazine (SMT), a widely used antibacterial, frequently contaminates freshwater ecosystems due to its high excretion in unchanged form during infection treatments. This study investigates a photocatalyst combining activated carbon (AC), graphene oxide (GO), and titanium dioxide (TiO2) for SMT degradation. Among the prepared materials, AC/GO/TiO2 synthesized under acidic conditions (pH 4) achieved 95 % degradation of SMT within 80 min under UV light irradiation. This performance is attributed to its high surface area (170 m2/g), efficient electron transfer, and reduced electron-hole recombination. Acid treatment significantly enhanced the interaction between TiO2 and the AC/GO matrix, as evidenced by SEM-EDS and XPS analyses, which revealed the formation of Ti–O–C bonds. Structural characterization through XRD, Rietveld refinement, and Raman spectroscopy confirmed the pure anatase phase with consistent crystalline domain sizes (∼13.7 nm), which is essential for sustained photocatalytic activity. Despite surface saturation during adsorption cycles, the photocatalyst maintained its structural integrity and degradation efficiency over four consecutive cycles, retaining its anatase crystallinity and Ti content. These results underscore the high stability, reusability, and effectiveness of synthesized material in degrading pharmaceutical contaminants. AC/GO/TiO2-prepared in acid conditions emerges as a promising candidate for wastewater treatment, industrial effluent management, and advanced oxidation processes, offering a sustainable water resource management and environmental protection solution.
{"title":"Efficient photocatalyst based on activated carbon/graphene oxide/TiO2 synthesized under acidic conditions for environmental remediation","authors":"Thais Aline Prado Mendonça, Amanda Soares Giroto, Julian Ticona Chambi, Silvia Lucia Cuffini, Nirton Cristi Silva Vieira, Maraísa Gonçalves","doi":"10.1016/j.jphotochem.2024.116244","DOIUrl":"10.1016/j.jphotochem.2024.116244","url":null,"abstract":"<div><div>Efficient materials are needed to address water contamination by pharmaceuticals, a growing environmental concern. Sulfamethazine (SMT), a widely used antibacterial, frequently contaminates freshwater ecosystems due to its high excretion in unchanged form during infection treatments. This study investigates a photocatalyst combining activated carbon (AC), graphene oxide (GO), and titanium dioxide (TiO<sub>2</sub>) for SMT degradation. Among the prepared materials, AC/GO/TiO<sub>2</sub> synthesized under acidic conditions (pH 4) achieved 95 % degradation of SMT within 80 min under UV light irradiation. This performance is attributed to its high surface area (170 m<sup>2</sup>/g), efficient electron transfer, and reduced electron-hole recombination. Acid treatment significantly enhanced the interaction between TiO<sub>2</sub> and the AC/GO matrix, as evidenced by SEM-EDS and XPS analyses, which revealed the formation of Ti–O–C bonds. Structural characterization through XRD, Rietveld refinement, and Raman spectroscopy confirmed the pure anatase phase with consistent crystalline domain sizes (∼13.7 nm), which is essential for sustained photocatalytic activity. Despite surface saturation during adsorption cycles, the photocatalyst maintained its structural integrity and degradation efficiency over four consecutive cycles, retaining its anatase crystallinity and Ti content. These results underscore the high stability, reusability, and effectiveness of synthesized material in degrading pharmaceutical contaminants. AC/GO/TiO<sub>2</sub>-prepared in acid conditions emerges as a promising candidate for wastewater treatment, industrial effluent management, and advanced oxidation processes, offering a sustainable water resource management and environmental protection solution.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"462 ","pages":"Article 116244"},"PeriodicalIF":4.1,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143166623","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-12-25DOI: 10.1016/j.jphotochem.2024.116242
Wen-Yuan Zhang , Yu-Xia Li , Wen-Le Zhang , Bo Wang , Xue-Qin Sun , Yu-Kui Hu , Jia-Cheng Liu
Porphyrin sensitizers were extensively studied due to their exceptional performance in dye-sensitized solar cells (DSSCs). In this study, three sensitizers (ZnP1, ZnP2, and ZnP3) with D-π-A structures containing heteroatom functional groups, such as triphenylamine, thianthrene and dibenzothiophene as electron donors, were designed and synthesized. The benzoic acid group, which functioned as an electron acceptor, and the strategically incorporated acetylene group enhance the light-harvesting abilities of the three sensitizers. Compared to ZnP2′s thianthrene and ZnP3′s dibenzothiophene, the incorporation of the triphenylamine electron donor in ZnP1 significantly improved electron transfer efficiency, short-circuit current density, and conversion efficiency. It also increased electron recombination resistance and prolonged electron lifetime, resulting in the best performance. Density functional theory (DFT) calculations confirmed these experimental findings.
{"title":"Synthesis of zinc porphyrin sensitizers containing heteroatoms and polybenzene ring donor groups for dye-sensitized solar cells","authors":"Wen-Yuan Zhang , Yu-Xia Li , Wen-Le Zhang , Bo Wang , Xue-Qin Sun , Yu-Kui Hu , Jia-Cheng Liu","doi":"10.1016/j.jphotochem.2024.116242","DOIUrl":"10.1016/j.jphotochem.2024.116242","url":null,"abstract":"<div><div>Porphyrin sensitizers were extensively studied due to their exceptional performance in dye-sensitized solar cells (DSSCs). In this study, three sensitizers (ZnP1, ZnP2, and ZnP3) with D-π-A structures containing heteroatom functional groups, such as triphenylamine, thianthrene and dibenzothiophene as electron donors, were designed and synthesized. The benzoic acid group, which functioned as an electron acceptor, and the strategically incorporated acetylene group enhance the light-harvesting abilities of the three sensitizers. Compared to ZnP2′s thianthrene and ZnP3′s dibenzothiophene, the incorporation of the triphenylamine electron donor in ZnP1 significantly improved electron transfer efficiency, short-circuit current density, and conversion efficiency. It also increased electron recombination resistance and prolonged electron lifetime, resulting in the best performance. Density functional theory (DFT) calculations confirmed these experimental findings.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"462 ","pages":"Article 116242"},"PeriodicalIF":4.1,"publicationDate":"2024-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143166618","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-12-25DOI: 10.1016/j.jphotochem.2024.116235
Miaoyan Hu , Peipei Zhang , Taohong Li , Kai Liu , Hailan Lian , Changyan Xu
Hydrothermal method became the main preparation method of the biomass carbon quantum dots (CQDs) by virtue of its strong operability and eco-friendliness. However, due to the differences of carbon precursors’ composition and the lack of statistical analysis of data in the synthesis process, hydrothermal synthesis process optimization was seriously insufficient, which had become the bottleneck of high − quality preparation and application of biomass CQDs. In this paper, the response surface methodology (RSM) was applied to optimize the hydrothermal synthesis process of Lophatherum gracile-based CQDs, so as to regulate the CQDs’ structure and properties by simply changing the synthesis parameters. In addition, the formation mechanism and fluorescence mechanism of the CQDs were interpreted by Materials Studio (MS) and density functional theory (DFT); and the morphology, FTIR spectrum, XPS spectrum, Zeta potential, fluorescence spectrum, UV–Vis absorption spectrum and fluorescence lifetime of the target CQDs were used to verify the interpretation. In coumarin parent nucleus, by introducing strong electron-donating groups such as amino and hydroxyl groups at C6&C7 and electron-withdrawing groups such as siloxy and aldehyde groups at C3&C4, the whole molecule formed a push–pull electron system, thus enhancing excitation-dependent fluorescence of CQDs. Finally, based on the good water solubility, fluorescence excitation dependence and fluorescence stability of the target CQDs, it was proved that the Lophatherum gracile-based CQDs had great application potential in fluorescence anti-counterfeiting. This study provided a new way for the high-value utilization of Lophatherum gracile.
{"title":"Optimization of the hydrothermal synthesis process and its formation mechanism and fluorescence mechanism of Lophatherum gracile-based CQDs","authors":"Miaoyan Hu , Peipei Zhang , Taohong Li , Kai Liu , Hailan Lian , Changyan Xu","doi":"10.1016/j.jphotochem.2024.116235","DOIUrl":"10.1016/j.jphotochem.2024.116235","url":null,"abstract":"<div><div>Hydrothermal method became the main preparation method of the biomass carbon quantum dots (CQDs) by virtue of its strong operability and eco-friendliness. However, due to the differences of carbon precursors’ composition and the lack of statistical analysis of data in the synthesis process, hydrothermal synthesis process optimization was seriously insufficient, which had become the bottleneck of high − quality preparation and application of biomass CQDs. In this paper, the response surface methodology (RSM) was applied to optimize the hydrothermal synthesis process of <em>Lophatherum gracile-based</em> CQDs, so as to regulate the CQDs’ structure and properties by simply changing the synthesis parameters. In addition, the formation mechanism and fluorescence mechanism of the CQDs were interpreted by Materials Studio (MS) and density functional theory (DFT); and the morphology, FTIR spectrum, XPS spectrum, Zeta potential, fluorescence spectrum, UV–Vis absorption spectrum and fluorescence lifetime of the target CQDs were used to verify the interpretation. In coumarin parent nucleus, by introducing strong electron-donating groups such as amino and hydroxyl groups at C6&C7 and electron-withdrawing groups such as siloxy and aldehyde groups at C3&C4, the whole molecule formed a push–pull electron system, thus enhancing excitation-dependent fluorescence of CQDs. Finally, based on the good water solubility, fluorescence excitation dependence and fluorescence stability of the target CQDs, it was proved that the <em>Lophatherum gracile-based</em> CQDs had great application potential in fluorescence anti-counterfeiting. This study provided a new way for the high-value utilization of <em>Lophatherum gracile</em>.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"462 ","pages":"Article 116235"},"PeriodicalIF":4.1,"publicationDate":"2024-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143166281","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-12-21DOI: 10.1016/j.jphotochem.2024.116232
Yonghe Liao , Tingzhuang Yi , Xiaoyan Su , Shuixiu Chen , Mingyue Lu , Xianxian Huang , Yanchun Yang , Xiangqing Qin , Chunli Tang , Yiheng Zhao , Hong Huang , Junjie Tan , Zhiming Yan , Neng Jiang
Hypochlorous acid (HClO) is a crucial endogenous reactive oxygen species (ROS) that is widely regarded as a representative of ROS. The excessive accumulation of HClO has been intimately linked to tissue damage and a myriad of diseases. Notably, mitochondria, the primary energy factories within cells, also serve as crucial sites for the generation of HClO. Consequently, the detection of intracellular mitochondrial HClO holds significant importance. In this study, we have designed and synthesized a novel near-infrared fluorescence (NIRF)/photoacoustic (PA) dual-modality probe, designated as MB-TPP. MB-TPP exhibits outstanding selectivity towards HClO, rapid fluorescence switching response (< 5 s). MB-TPP demonstrates remarkable sensitivity for HClO detection (LOD = 0.075 μM). Furthermore, MB-TPP possesses favorable water solubility and mitochondrial targeting capability. The application of MB-TPP has been validated in biological models such as zebrafish and mice, where it achieves excellent NIRF imaging of endogenous and exogenous HClO. Remarkably, MB-TPP possesses the capability to perform PA imaging of HClO ex vivo, exhibiting a linear detection efficiency. Moreover, MB-TPP demonstrated its capability for NIRF/PA dual-modality imaging in the mice model of rheumatoid arthritis. As a powerful NIRF/PA imaging visualization tool, MB-TPP holds immense promise for monitoring and investigating HClO-related inflammatory diseases, particularly those associated with mitochondrial function in biological contexts, thereby underscoring its broad application potential and significant value in the fields of biomedical research and clinical diagnostics.
{"title":"A Mitochondria-Targeted Fluorescence/Photoacoustic Dual-Modality imaging probe for Hypochlorous Acid-Related inflammatory Responses in vivo","authors":"Yonghe Liao , Tingzhuang Yi , Xiaoyan Su , Shuixiu Chen , Mingyue Lu , Xianxian Huang , Yanchun Yang , Xiangqing Qin , Chunli Tang , Yiheng Zhao , Hong Huang , Junjie Tan , Zhiming Yan , Neng Jiang","doi":"10.1016/j.jphotochem.2024.116232","DOIUrl":"10.1016/j.jphotochem.2024.116232","url":null,"abstract":"<div><div>Hypochlorous acid (HClO) is a crucial endogenous reactive oxygen species (ROS) that is widely regarded as a representative of ROS. The excessive accumulation of HClO has been intimately linked to tissue damage and a myriad of diseases. Notably, mitochondria, the primary energy factories within cells, also serve as crucial sites for the generation of HClO. Consequently, the detection of intracellular mitochondrial HClO holds significant importance. In this study, we have designed and synthesized a novel near-infrared fluorescence (NIRF)/photoacoustic (PA) dual-modality probe, designated as MB-TPP. MB-TPP exhibits outstanding selectivity towards HClO, rapid fluorescence switching response (< 5 s). MB-TPP demonstrates remarkable sensitivity for HClO detection (<em>LOD</em> = 0.075 μM). Furthermore, MB-TPP possesses favorable water solubility and mitochondrial targeting capability. The application of MB-TPP has been validated in biological models such as zebrafish and mice, where it achieves excellent NIRF imaging of endogenous and exogenous HClO. Remarkably, MB-TPP possesses the capability to perform PA imaging of HClO <em>ex vivo</em>, exhibiting a linear detection efficiency. Moreover, MB-TPP demonstrated its capability for NIRF/PA dual-modality imaging in the mice model of rheumatoid arthritis. As a powerful NIRF/PA imaging visualization tool, MB-TPP holds immense promise for monitoring and investigating HClO-related inflammatory diseases, particularly those associated with mitochondrial function in biological contexts, thereby underscoring its broad application potential and significant value in the fields of biomedical research and clinical diagnostics.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"462 ","pages":"Article 116232"},"PeriodicalIF":4.1,"publicationDate":"2024-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143166277","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-12-20DOI: 10.1016/j.jphotochem.2024.116241
Haoran Hu, Chen Chen, Siyi Wei, Chong Zhang, Chao Gao, Chengguo Sun, Yang Du, Bingcheng Hu
Iminoheteroarenes are more convenient to synthesize compared to other photochromic molecules. Here we presented a series of pyrazole based imines photoswitches (including aryliminopyrazoles and iminobispyrazole). Aryliminopyrazoles without stable photoswitching while iminobispyrazoles exhibted thermal half-lives from 3.6 to 5.6 mins and optical fatigue resistance, which provided theoretical and practical basis for the design of exploiting novel imines photoswitches.
{"title":"Unmodified iminobispyrazole scaffold as imines photoswitches with stable photoswitching behavior","authors":"Haoran Hu, Chen Chen, Siyi Wei, Chong Zhang, Chao Gao, Chengguo Sun, Yang Du, Bingcheng Hu","doi":"10.1016/j.jphotochem.2024.116241","DOIUrl":"10.1016/j.jphotochem.2024.116241","url":null,"abstract":"<div><div>Iminoheteroarenes are more convenient to synthesize compared to other photochromic molecules. Here we presented a series of pyrazole based imines photoswitches (including aryliminopyrazoles and iminobispyrazole). Aryliminopyrazoles without stable photoswitching while iminobispyrazoles exhibted thermal half-lives from 3.6 to 5.6 mins and optical fatigue resistance, which provided theoretical and practical basis for the design of exploiting novel imines photoswitches.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"462 ","pages":"Article 116241"},"PeriodicalIF":4.1,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143166600","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-12-20DOI: 10.1016/j.jphotochem.2024.116227
Abdessalim Chahid , Brahim Zahraoui , Driss Lahcene , Francisco Boscá , María Luisa Marín
Quartz sand collected from the dunes of Taghit, a region of Bechar in southwestern Algeria, served a dual purpose in this study. Firstly, it acted as a natural support for the TiO2 photocatalyst. Secondly, it served as a low-cost precursor for silica extraction through an alkaline fusion process. TiO2 nanoparticles were efficiently immobilized on both Dune Sand (TiO2-DS) and extracted silica (TiO2-SP) using an organometallic coating approach, providing a versatile TiO2-based photocatalyst solution. Characterizing the prepared catalysts included techniques such as ICP, N2 adsorption XRD, FTIR, FESEM, and XPS. It was noted that TiO2 exhibited a well-coated layer on both dune sand and extracted silica, demonstrating a prominent anatase crystalline phase. Chemical composition analysis revealed the presence of chemical bonds between Ti and Si in the TiO2-SP and TiO2-DS samples. Moreover, TiO2 particles showed improved dispersion on the surface of TiO2-SP compared to TiO2-DS due to the larger specific surface area of the extracted silica resulting in SBET of 83.74 m2.g−1 for TiO2-SP compared to 30.15 m2.g−1 for TiO2-DS. The photocatalytic performance of TiO2-DS and TiO2-SP was compared to P25 in the abatement of three common pharmaceutical compounds: amoxicillin (AMO), ibuprofen (IBU), and acetaminophen (ACT), with a focus on the influence of the support material on photoactivity. TiO2-SP exhibited a slight advantage in terms of mineralization with 90 %, 92 %, and 99 % after 300 min for ACT, AMO, and IBU, respectively, Whereas the TiO2-DS catalyst resulted in slightly lower results of 81 %, 85 %, and 97 % for the same drugs over the same irradiation period. Additionally, both TiO2-SP and TiO2-DS demonstrated easy separation from the reaction medium by quick sedimentation upon agitation cessation. In contrast, P25 remained in a colloidal suspension.
{"title":"Photocatalytic degradation of pharmaceuticals using natural sand-based TiO2 catalysts: Preparation, characterization, and reactivity","authors":"Abdessalim Chahid , Brahim Zahraoui , Driss Lahcene , Francisco Boscá , María Luisa Marín","doi":"10.1016/j.jphotochem.2024.116227","DOIUrl":"10.1016/j.jphotochem.2024.116227","url":null,"abstract":"<div><div>Quartz sand collected from the dunes of Taghit, a region of Bechar in southwestern Algeria, served a dual purpose in this study. Firstly, it acted as a natural support for the TiO<sub>2</sub> photocatalyst. Secondly, it served as a low-cost precursor for silica extraction through an alkaline fusion process. TiO<sub>2</sub> nanoparticles were efficiently immobilized on both Dune Sand (TiO<sub>2</sub>-DS) and extracted silica (TiO<sub>2</sub>-SP) using an organometallic coating approach, providing a versatile TiO<sub>2</sub>-based photocatalyst solution. Characterizing the prepared catalysts included techniques such as ICP, N<sub>2</sub> adsorption XRD, FTIR, FESEM, and XPS. It was noted that TiO<sub>2</sub> exhibited a well-coated layer on both dune sand and extracted silica, demonstrating a prominent anatase crystalline phase. Chemical composition analysis revealed the presence of chemical bonds between Ti and Si in the TiO<sub>2</sub>-SP and TiO<sub>2</sub>-DS samples. Moreover, TiO<sub>2</sub> particles showed improved dispersion on the surface of TiO<sub>2</sub>-SP compared to TiO<sub>2</sub>-DS due to the larger specific surface area of the extracted silica resulting in S<sub>BET</sub> of 83.74 m<sup>2</sup>.g<sup>−1</sup> for TiO<sub>2</sub>-SP compared to 30.15 m<sup>2</sup>.g<sup>−1</sup> for TiO<sub>2</sub>-DS. The photocatalytic performance of TiO<sub>2</sub>-DS and TiO<sub>2</sub>-SP was compared to P25 in the abatement of three common pharmaceutical compounds: amoxicillin (AMO), ibuprofen (IBU), and acetaminophen (ACT), with a focus on the influence of the support material on photoactivity. TiO<sub>2</sub>-SP exhibited a slight advantage in terms of mineralization with 90 %, 92 %, and 99 % after 300 min for ACT, AMO, and IBU, respectively, Whereas the TiO<sub>2</sub>-DS catalyst resulted in slightly lower results of 81 %, 85 %, and 97 % for the same drugs over the same irradiation period. Additionally, both TiO<sub>2</sub>-SP and TiO<sub>2</sub>-DS demonstrated easy separation from the reaction medium by quick sedimentation upon agitation cessation. In contrast, P25 remained in a colloidal suspension.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"462 ","pages":"Article 116227"},"PeriodicalIF":4.1,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143166607","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-12-19DOI: 10.1016/j.jphotochem.2024.116239
Lourdes Gotopo , Gustavo Cabrera , Angel H. Romero
The α-effect is a mysterious phenomenon of the organic chemistry that allow to explain the significant reactivity of nucleophiles featuring an α-substituent. Its determination often requires of extensive kinetic analysis or studies in gas phase as well as the use of specific chemical reactions and specialized substrates. Herein we reported a simple and rapid strategy to validate the nucleophilicity and nucleophilic α-effect from simple steady state fluorescence measurements at room temperature with minimal sample and time requirements using a convenient fluorophore featuring an σ-hole region. The key points were the use of a fluorophore having a high intramolecular charge-transfer (ICT) and an electrophilic acceptor moiety along the donor (D)-acceptor (A) chain. The interaction of the nucleophile with the acceptor group upon excitation promoted a selective quenching that was dependent on the nucleophilicity of the nucleophile, whereas the existence of the ICT enhanced the selectivity and strength of the quenching response. It allowed us to generate a nucleophilic trend and recognize cases of α-effect. A broad number of nucleophiles from anionic species to neutral nucleophiles was analyzed. Also, we introduced the concept of “nucleophilic β, γ- and δ-effects” for interpreting the over-nucleophilicity of some “β-, γ- and δ-nucleophiles”. A general interpretation of the anomalous nucleophilic effects based on the extra stabilization of transition-state was provided. The intermolecular interaction between nucleophile and acceptor moiety was theoretically and experimentally supported. Our strategy opens new perspective for quantifying the nucleophilicity and their anomalous effects based on the recognition of non-covalent interaction using fluorometry as key technique.
{"title":"Estimation of the nucleophilic α- and their relative β-, γ- and δ-effects in solution through fluorometry","authors":"Lourdes Gotopo , Gustavo Cabrera , Angel H. Romero","doi":"10.1016/j.jphotochem.2024.116239","DOIUrl":"10.1016/j.jphotochem.2024.116239","url":null,"abstract":"<div><div>The <em>α-</em>effect is a mysterious phenomenon of the organic chemistry that allow to explain the significant reactivity of nucleophiles featuring an <em>α-</em>substituent. Its determination often requires of extensive kinetic analysis or studies in gas phase as well as the use of specific chemical reactions and specialized substrates. Herein we reported a simple and rapid strategy to validate the nucleophilicity and nucleophilic <em>α</em>-effect from simple steady state fluorescence measurements at room temperature with minimal sample and time requirements using a convenient fluorophore featuring an σ-hole region. The key points were the use of a fluorophore having a high intramolecular charge-transfer (ICT) and an electrophilic acceptor moiety along the donor (D)-acceptor (A) chain. The interaction of the nucleophile with the acceptor group upon excitation promoted a selective quenching that was dependent on the nucleophilicity of the nucleophile, whereas the existence of the ICT enhanced the selectivity and strength of the quenching response. It allowed us to generate a nucleophilic trend and recognize cases of <em>α-</em>effect. A broad number of nucleophiles from anionic species to neutral nucleophiles was analyzed. Also, we introduced the concept of “nucleophilic <em>β, γ-</em> and <em>δ</em>-effects” for interpreting the over-nucleophilicity of some “<em>β-, γ-</em> and <em>δ</em>-nucleophiles”. A general interpretation of the anomalous nucleophilic effects based on the extra stabilization of transition-state was provided. The intermolecular interaction between nucleophile and acceptor moiety was theoretically and experimentally supported. Our strategy opens new perspective for quantifying the nucleophilicity and their anomalous effects based on the recognition of non-covalent interaction using fluorometry as key technique.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"462 ","pages":"Article 116239"},"PeriodicalIF":4.1,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143166621","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-12-18DOI: 10.1016/j.jphotochem.2024.116221
Xupeng Chen , Jun Yu , Yong Jin , Yunzhao Zhang , Jie He , Xingang Li , Chun Zhang
In this paper, C/ZnO/ZnFe2O4@ZnIn2S4 ternary heterojunctions were prepared using Zn-Fe bimetal-organic frameworks (Zn-Fe MOFs) as precursors and applied to the photocatalytic degradation of tetracycline hydrochloride (TC). The experimental results show that 30 mg of the composite (FS-2) showed 96 % removal of 20 mg/L TC. The improved photocatalytic performance was attributed to the synergistic effect of the double S-scheme heterojunction and the carbon layer, which greatly facilitated the separation of electron-hole pairs by the reverse motion of electrons and holes driven by the difference of work functions and the built-in electric field at the interface. The carbon layer acts as an electronic bridge can further improve the charge transfer between the interfaces of different photocatalysts, allowing more useful electrons and holes with strong redox capabilities to participate in the surface reactions. Combining the experimental results and density functional theory (DFT) calculations, the photocatalytic mechanism of the dual S-scheme system is proposed. This study provides a theoretical basis for the design of novel photocatalytic materials with dual S-scheme heterojunctions and efficient photocatalytic degradation.
{"title":"Novel C/ZnO/ZnFe2O4@ZnIn2S4 double S-scheme heterojunction for efficient photocatalytic degradation of tetracycline hydrochloride","authors":"Xupeng Chen , Jun Yu , Yong Jin , Yunzhao Zhang , Jie He , Xingang Li , Chun Zhang","doi":"10.1016/j.jphotochem.2024.116221","DOIUrl":"10.1016/j.jphotochem.2024.116221","url":null,"abstract":"<div><div>In this paper, C/ZnO/ZnFe<sub>2</sub>O<sub>4</sub>@ZnIn<sub>2</sub>S<sub>4</sub> ternary heterojunctions were prepared using Zn-Fe bimetal-organic frameworks (Zn-Fe MOFs) as precursors and applied to the photocatalytic degradation of tetracycline hydrochloride (TC). The experimental results show that 30 mg of the composite (FS-2) showed 96 % removal of 20 mg/L TC. The improved photocatalytic performance was attributed to the synergistic effect of the double S-scheme heterojunction and the carbon layer, which greatly facilitated the separation of electron-hole pairs by the reverse motion of electrons and holes driven by the difference of work functions and the built-in electric field at the interface. The carbon layer acts as an electronic bridge can further improve the charge transfer between the interfaces of different photocatalysts, allowing more useful electrons and holes with strong redox capabilities to participate in the surface reactions. Combining the experimental results and density functional theory (DFT) calculations, the photocatalytic mechanism of the dual S-scheme system is proposed. This study provides a theoretical basis for the design of novel photocatalytic materials with dual S-scheme heterojunctions and efficient photocatalytic degradation.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"462 ","pages":"Article 116221"},"PeriodicalIF":4.1,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143166270","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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