Journal of Photochemistry and Photobiology A-chemistry最新文献

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Fabrication of photochromic spiropyran-based coatings for smart color-tunable textiles 智能可调色纺织品用光致变色螺吡喃涂料的制备
IF 4.1 3区 化学
Journal of Photochemistry and Photobiology A-chemistry Pub Date : 2025-06-18 DOI: 10.1016/j.jphotochem.2025.116583
Shaorong Yang, Jiangbo Hui, Tong Xue, Chaoxia Wang, Yunjie Yin
{"title":"Fabrication of photochromic spiropyran-based coatings for smart color-tunable textiles","authors":"Shaorong Yang,&nbsp;Jiangbo Hui,&nbsp;Tong Xue,&nbsp;Chaoxia Wang,&nbsp;Yunjie Yin","doi":"10.1016/j.jphotochem.2025.116583","DOIUrl":"10.1016/j.jphotochem.2025.116583","url":null,"abstract":"<div><div>Photochromic materials have gained broad attention in a wide variety of fields due to their dynamic color transition properties. However, the high sensitivity and fast response of these materials still require further exploration. To address this challenge, a new photochromic spiropyran compound (SP-Br) was developed and successfully synthesized by incorporating a long alkyl chain into the spiropyran structure, achieving an optimal hydrophilic-lipophilic balance (HLB). The resulting SP-Br was applied to cotton fabric substrates through a simple screen-printing process, yielding a photochromic cotton fabric (SP-CF) with a functional coating capable of reversible color transitions. It is reported that SP-Br undergoes a reversible ring-opening/ring-closing isomerization when exposed to UV radiation at 365 nm. And with the color of the SP-CF reaching its maximum intensity within 30 s of UV exposure. After 10 color transition cycles, a slight reduction in the absorbance of the photochromic coated cotton fabric was observed; while its fatigue resistance remained virtually unaffected. Moreover, the screen-printed photochromic cotton fabric fabricated through this method exhibits several notable advantages, including rapid response time, excellent reversibility, significant color-changing ability, superior tunability in coloration, and reusability. These characteristics render the material especially promising for applications in fields like anti-counterfeiting printing, UV protection, information encryption, pattern switching, and other related domains.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"469 ","pages":"Article 116583"},"PeriodicalIF":4.1,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144329548","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}
引用次数: 0
Visible-light photocatalytic activity of a green niobium pentoxide nanocatalyst: Experimental analysis and machine learning approach 绿色五氧化二铌纳米催化剂的可见光催化活性:实验分析和机器学习方法
IF 4.1 3区 化学
Journal of Photochemistry and Photobiology A-chemistry Pub Date : 2025-06-18 DOI: 10.1016/j.jphotochem.2025.116585
Hanna Abdalrahman Mahmud , Leandro Rodrigues Oviedo , Maurício Dalla Costa Rodrigues da Silva , Cristiane dos Santos , Giovani Pavoski , Jorge Alberto Soares Tenório , Denise Crocce Romano Espinosa , William Leonardo da Silva
{"title":"Visible-light photocatalytic activity of a green niobium pentoxide nanocatalyst: Experimental analysis and machine learning approach","authors":"Hanna Abdalrahman Mahmud ,&nbsp;Leandro Rodrigues Oviedo ,&nbsp;Maurício Dalla Costa Rodrigues da Silva ,&nbsp;Cristiane dos Santos ,&nbsp;Giovani Pavoski ,&nbsp;Jorge Alberto Soares Tenório ,&nbsp;Denise Crocce Romano Espinosa ,&nbsp;William Leonardo da Silva","doi":"10.1016/j.jphotochem.2025.116585","DOIUrl":"10.1016/j.jphotochem.2025.116585","url":null,"abstract":"<div><div>This work aims to develop green Nb<sub>2</sub>O<sub>5</sub>-NPs from <em>Carya illinoinensis</em> extract for the photodegradation of six organic dyes and to predict the reaction degradation progress through a machine learning study. 71.5 % removal was the highest value achieved for dye degradation after 120 min under visible radiation with the apparent rate of the pseudo first-order reaction <em>k</em> = 0.0034 min<sup>−1</sup>. DT algorithm showed satisfactory performance (R<sup>2</sup><sub>training</sub> = 0.9975 / R<sup>2</sup><sub>test</sub> = 0.9945, RMSE<sub>training</sub> = 0.059 / RMSE<sub>test</sub> = 0.094), predicting 75 % of MB dye removal after 300 min under visible radiation. Nb<sub>2</sub>O<sub>5</sub>-NPs showed high phytotoxicity for <em>Beta vulgaris</em> L. seeds (except at 50 mg L<sup>−1</sup>) and no phytotoxicity for <em>Brassica oleracea</em> seeds in all concentrations tested (12.5–100 mg L<sup>−1</sup>). Therefore, this study highlights the importance of integrating machine learning models into catalytic research, offering valuable insights for optimizing reaction conditions and guiding scalable photodegradation processes.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"469 ","pages":"Article 116585"},"PeriodicalIF":4.1,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144338387","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}
引用次数: 0
The regulation of π-linker aromaticity of thiophene derivatives on cyclization and ESPT reaction 噻吩衍生物的π-连接体芳香性对环化和ESPT反应的调节
IF 4.1 3区 化学
Journal of Photochemistry and Photobiology A-chemistry Pub Date : 2025-06-17 DOI: 10.1016/j.jphotochem.2025.116584
Xinyu Wang , Yingrui Yin , Xiaoyang Liu , Zuzhi Chen , Mingli Wang , Yunfan Yang
{"title":"The regulation of π-linker aromaticity of thiophene derivatives on cyclization and ESPT reaction","authors":"Xinyu Wang ,&nbsp;Yingrui Yin ,&nbsp;Xiaoyang Liu ,&nbsp;Zuzhi Chen ,&nbsp;Mingli Wang ,&nbsp;Yunfan Yang","doi":"10.1016/j.jphotochem.2025.116584","DOIUrl":"10.1016/j.jphotochem.2025.116584","url":null,"abstract":"<div><div>Recently, researchers studied how the aromaticity of π-linker affects cyclization reactions and found that varying aromaticity can regulate these reactions. Inspired by this, the different aromatic π-linker with proton donor-acceptor blocks will be investigated to explore the influence of aromaticity on cyclization and proton transfer reactions. In this work, the quantum chemical calculation combined with density functional theory (DFT) and the multi-configurational self-consistent field (MCSCF) methods are employed to unveil the photophysical and photochemical processes. The established potential energy curves (PECs) and the calculated minimum energy pathways (MEPs) indicate that the excited state proton transfer (ESPT) and photocyclization processes vary with different π-linker. The complete-active-space self-consistent-field (CASSCF) calculations reveal that a nonradiative channel will be opened via the conical intersection (CI) between the ground and the first excited states during photocyclization. The time evolved excited state nonadiabatic dynamics are simulated to demonstrate the ultrafast photocyclization reactions impede the ESPT. Finally, the aromaticity of various π-linker is evaluated using nucleus-independent chemical shifts (NICS) aromaticity indices. The study concludes that excited-state antiaromaticity relief facilitates the cyclization reaction and ESPT process.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"469 ","pages":"Article 116584"},"PeriodicalIF":4.1,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144322011","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}
引用次数: 0
Exploring photodiode characteristics of a D-π-D type organic semiconductor incorporating a fluorenyl π-bridge and triphenylamine donors 探讨含氟酰π桥和三苯胺给体的D-π-D型有机半导体的光电二极管特性
IF 4.1 3区 化学
Journal of Photochemistry and Photobiology A-chemistry Pub Date : 2025-06-16 DOI: 10.1016/j.jphotochem.2025.116532
Musa Erdoğan , Ali Rıza Deniz , Zakir Çaldıran
{"title":"Exploring photodiode characteristics of a D-π-D type organic semiconductor incorporating a fluorenyl π-bridge and triphenylamine donors","authors":"Musa Erdoğan ,&nbsp;Ali Rıza Deniz ,&nbsp;Zakir Çaldıran","doi":"10.1016/j.jphotochem.2025.116532","DOIUrl":"10.1016/j.jphotochem.2025.116532","url":null,"abstract":"<div><div>In this study, the design, synthesis, and spectroscopic characterization of a fluorene-based electron-rich D-π-D type organic semiconductor material 4,4′-((9<em>H</em>-fluoren-9-ylidene)methylene)bis(<em>N</em>,<em>N</em>-diphenylaniline), namely TPA2, were achieved by selecting triphenylamine (TPA) as the donor group. The Au/TPA2/p-Si/Al photodiode fabricated using TPA2 organic material as interface material. The electrical and optical properties of photodiode were investigated. The SEM and AFM images of the TPA2/p-Si thin film were analyzed. Also, UV–Vis absorption spectra measurement of the thin film was analyzed. The current–voltage (I-V) measurements of the diode were performed for different light intensity values. Electrical paremeters [ideality factor (n) and barrier height (Φ<sub>b</sub>), rectification rates (RR), saturation current (I<sub>0</sub>)] and photodiode parameters [photocurrent (I<sub>ph</sub>), photosensitivity (S), photoresponse (R), detectivity (D*)] of the diode were calculated using the I-V measurements of the diode. With increasing light intensity between 0 mW/cm<sup>2</sup> and 100 mW/cm<sup>2</sup> light intensity, the n values varies between 1.41 and 2.14, the Φ<sub>b</sub> values varies between 0.81 and 0.66, the R<sub>s</sub> values varies between 171 Ω and 1487 Ω and the RR values varies between 196.2 and 42.4. The calculated fundamental electrical and photodiode parameters showed that TPA2 material improved the electrical and optical parameters. The analyzed experimental results show that the Au/TPA2/p-Si/Al diode exhibits a good photodiode behavior under various light intensities and this diode can be used in optoelectronic devices.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"469 ","pages":"Article 116532"},"PeriodicalIF":4.1,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144313182","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}
引用次数: 0
Excitation-dependent room temperature phosphorescence carbon dots with ultralong lifetime for information encryption and delay illumination 超长寿命室温磷光碳点用于信息加密和延迟照明
IF 4.1 3区 化学
Journal of Photochemistry and Photobiology A-chemistry Pub Date : 2025-06-15 DOI: 10.1016/j.jphotochem.2025.116577
Wenjing Chen , Xi Yang , Shujuan Liu , Yi Zhu , Haoyan Zhen , Jizu Yang , Shuguang Li , Jianxin Xie , Jing Yang , Zhengjun Shi
{"title":"Excitation-dependent room temperature phosphorescence carbon dots with ultralong lifetime for information encryption and delay illumination","authors":"Wenjing Chen ,&nbsp;Xi Yang ,&nbsp;Shujuan Liu ,&nbsp;Yi Zhu ,&nbsp;Haoyan Zhen ,&nbsp;Jizu Yang ,&nbsp;Shuguang Li ,&nbsp;Jianxin Xie ,&nbsp;Jing Yang ,&nbsp;Zhengjun Shi","doi":"10.1016/j.jphotochem.2025.116577","DOIUrl":"10.1016/j.jphotochem.2025.116577","url":null,"abstract":"<div><div>Long-lifetime room temperature phosphorescent (RTP) carbon dots (CDs) have received extensive attention due to their potential applications in fields such as information encryption, sensing, and biological imaging. However, the rapid synthesis of RTP carbon dots with excitation wavelength dependence remains a challenge. Herein, Zn-CDs@B<sub>2</sub>O<sub>3</sub> with excitation wavelength dependence were prepared by calcining a mixture of biuret, boric acid and zinc sulfate at 250 ℃ for 30 min. CDs are embedded into the rigid matrix (B<sub>2</sub>O<sub>3</sub>) through covalent bonds (B-C), which suppresses the non-radiative transitions and molecular vibrations of the CDs. The incorporation of N, O, B, and Zn atoms enhances intersystem crossing (ISC) and increases the spin–orbit coupling (SOC), the phosphorescence lifetime of Zn-CDs@B<sub>2</sub>O<sub>3</sub> reaches up to 1.23 s. The Zn-CDs@B<sub>2</sub>O<sub>3</sub> composite is notable for its vivid blue RTP under 254 nm excitation, visible for about 13 s, and it shifts to a bright green RTP excitated at 365 nm, lasting 8 s to the naked eye. The experimental results indicate that the excitation wavelength dependence of Zn-CDs@B<sub>2</sub>O<sub>3</sub> may be attributed to the presence of multiple luminescent centers. Based on the aforementioned characteristics, the Zn-CDs@B<sub>2</sub>O<sub>3</sub> were successfully used in the advanced information encryption and light emitting diodes (LEDs), the Zn-CDs@B<sub>2</sub>O<sub>3</sub> show considerable promise for applications in information encryption and delay illumination.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"469 ","pages":"Article 116577"},"PeriodicalIF":4.1,"publicationDate":"2025-06-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144321855","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}
引用次数: 0
Gamma irradiation effects on the characteristics of Sm3+ doped aluminate phosphors for dosimetry applications 辐照对剂量学应用中Sm3+掺杂铝酸盐荧光粉特性的影响
IF 4.1 3区 化学
Journal of Photochemistry and Photobiology A-chemistry Pub Date : 2025-06-14 DOI: 10.1016/j.jphotochem.2025.116578
Tejas , R. Sharanya , Kalpataru Panda , Naregundi Karunakara , M.I. Sayyed , Aljawhara H. Almuqrin , Dinesh Negi , Sudha D. Kamath
{"title":"Gamma irradiation effects on the characteristics of Sm3+ doped aluminate phosphors for dosimetry applications","authors":"Tejas ,&nbsp;R. Sharanya ,&nbsp;Kalpataru Panda ,&nbsp;Naregundi Karunakara ,&nbsp;M.I. Sayyed ,&nbsp;Aljawhara H. Almuqrin ,&nbsp;Dinesh Negi ,&nbsp;Sudha D. Kamath","doi":"10.1016/j.jphotochem.2025.116578","DOIUrl":"10.1016/j.jphotochem.2025.116578","url":null,"abstract":"<div><div>This study investigates the synthesis, optical, and Thermoluminescent properties of orangish-red emitting SrAl<sub>2</sub>O<sub>4</sub> phosphors doped with Sm<sup>3+</sup> ions, prepared via the solid-state reaction technique. The resulting phosphors exhibit a monoclinic crystal structure, belonging to the P2/m space group, as confirmed by X-ray diffraction. Scanning Electron Microscopy (SEM) analysis reveals significant surface agglomeration, while Energy Dispersive X-ray (EDX) spectroscopy validates the composition of the phosphors. Fourier Transform Infrared (FTIR) spectroscopy indicates the presence of various functional groups in the sample. Reflectance spectra reveal a decrease in bandgap on doping. CIE coordinates further demonstrate that the phosphors are appropriate candidates for reddish light-emitting diode (LED) applications since they exhibit emission peaks at 562 nm, 599 nm, and 645 nm under UV excitation, which are associated with green and red emissions. The optimal concentration of Sm<sup>3+</sup> is 0.9 mol%, beyond which the concentration quenching of luminescence takes place. The SrAl<sub>2</sub>O<sub>4</sub>: 0.9 mol% Sm<sup>3+</sup> phosphor displays a linear response to radiation doses ranging from 5 Gy to 25 Gy, with an optimal dose of 10 Gy. The phosphor also exhibits high sensitivity, capable of detecting low doses of radiation. Thermoluminescence (TL) analysis reveals three trap centers with different energies, indicating the potential of these phosphors for use as TL dosimeters. The findings suggest that Sm<sup>3+</sup>-doped SrAl<sub>2</sub>O<sub>4</sub> phosphors are promising for both LED and radiation dosimetry applications.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"469 ","pages":"Article 116578"},"PeriodicalIF":4.1,"publicationDate":"2025-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144313181","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}
引用次数: 0
Corrigendum to “Hydrogen-bonding locked phenanthro[9,10-d]imidazole-anthracene emitter enables high-luminance blue OLEDs with low efficiency roll-off” [J. Photochem. Photobiol. A: Chem. 468 (2025) 116539] “氢键锁定菲唑[9,10-d]咪唑-蒽发射器实现低效率滚转的高亮度蓝色oled”的更正[J]。Photochem。Photobiol。A:化学,468 (2025)116539]
IF 4.1 3区 化学
Journal of Photochemistry and Photobiology A-chemistry Pub Date : 2025-06-14 DOI: 10.1016/j.jphotochem.2025.116562
Ying Ji , Kaijun Xu , Jingru Zhou , Bingyue Wang , Chenglin Ma , Jiadong Zhou , Shanfeng Xue , Xu Qiu
{"title":"Corrigendum to “Hydrogen-bonding locked phenanthro[9,10-d]imidazole-anthracene emitter enables high-luminance blue OLEDs with low efficiency roll-off” [J. Photochem. Photobiol. A: Chem. 468 (2025) 116539]","authors":"Ying Ji ,&nbsp;Kaijun Xu ,&nbsp;Jingru Zhou ,&nbsp;Bingyue Wang ,&nbsp;Chenglin Ma ,&nbsp;Jiadong Zhou ,&nbsp;Shanfeng Xue ,&nbsp;Xu Qiu","doi":"10.1016/j.jphotochem.2025.116562","DOIUrl":"10.1016/j.jphotochem.2025.116562","url":null,"abstract":"","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"469 ","pages":"Article 116562"},"PeriodicalIF":4.1,"publicationDate":"2025-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144633395","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}
引用次数: 0
Oxygenation is the main pathway for the reaction between superoxide anion and tryptophan radical 氧合是超氧阴离子与色氨酸自由基反应的主要途径
IF 4.1 3区 化学
Journal of Photochemistry and Photobiology A-chemistry Pub Date : 2025-06-14 DOI: 10.1016/j.jphotochem.2025.116571
Yuliya S. Zhuravleva , Petr S. Sherin
{"title":"Oxygenation is the main pathway for the reaction between superoxide anion and tryptophan radical","authors":"Yuliya S. Zhuravleva ,&nbsp;Petr S. Sherin","doi":"10.1016/j.jphotochem.2025.116571","DOIUrl":"10.1016/j.jphotochem.2025.116571","url":null,"abstract":"<div><div>Oxygenation, the covalent addition of oxygen, is the most common chemical modification of proteins, leading to the loss of their structure and functionality. Tryptophan (TrpH) within peptides and proteins is considered one of the main sources of electrons for cellular oxidants, and corresponding tryptophan radicals may have long lifetimes. The reaction between superoxide anion (O<sub>2</sub><sup>•—</sup>) and tryptophan radicals (Trp<sup>•</sup>) is the fastest known bimolecular reaction of Trp<sup>•</sup>, which may lead to the irreversible oxygenation of TrpH. This reaction may proceed via the <em>addition,</em> yielding oxygenated forms of TrpH, or the <em>electron transfer</em> with the restoration of the initial reagents. Currently, the mechanism of this reaction remains unclear due to contradicting conclusions reported previously. This work aims to elucidate the mechanism of this reaction using methods of time-resolved optical spectroscopy to visualise processes on the microsecond time scale and liquid chromatography-mass spectrometry to analyse the reagent degradation and product accumulation. The target radicals were generated using natural photosensitiser kynurenic acid irradiated by pulsed laser radiation. Our time-resolved data demonstrated that TrpH undergoes rapid oxygenation under aerobic conditions without significant restoration of its ground state. Hydroxyperoxides and N-formyl-kynurenine were found to be major photoproducts of TrpH degradation. Altogether, our data unambiguously indicated the <em>addition</em> as the major pathway for the reaction between superoxide anion and tryptophan radicals. Comparison of experimentally measured yields of reagent degradation with those calculated from the kinetic scheme provided an opportunity to estimate the ratio between addition/electron transfer reactions as 7/1 for N-acetyl-L-tryptophan.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"469 ","pages":"Article 116571"},"PeriodicalIF":4.1,"publicationDate":"2025-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144522255","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}
引用次数: 0
Dft-guided investigation on the photothermal DMC synthesis mechanism from CO2 and CH3OH over tetragonal ZrO2(101) with oxygen vacancies dft引导下氧空位四方ZrO2(101)上CO2和CH3OH光热合成DMC机理的研究
IF 4.1 3区 化学
Journal of Photochemistry and Photobiology A-chemistry Pub Date : 2025-06-13 DOI: 10.1016/j.jphotochem.2025.116582
Xiaoyang Wang , Le Liu , Xiushuai Guan , Xiaochao Zhang , Xiaokun Wang , Xiya Zhao , Juan Jia , Changming Zhang
{"title":"Dft-guided investigation on the photothermal DMC synthesis mechanism from CO2 and CH3OH over tetragonal ZrO2(101) with oxygen vacancies","authors":"Xiaoyang Wang ,&nbsp;Le Liu ,&nbsp;Xiushuai Guan ,&nbsp;Xiaochao Zhang ,&nbsp;Xiaokun Wang ,&nbsp;Xiya Zhao ,&nbsp;Juan Jia ,&nbsp;Changming Zhang","doi":"10.1016/j.jphotochem.2025.116582","DOIUrl":"10.1016/j.jphotochem.2025.116582","url":null,"abstract":"<div><div>In the context of global carbon neutrality, “green chemistry” has spurred the conversion of CO<sub>2</sub> into high-value-added dimethyl carbonates (DMC). Nevertheless, the theoretical exploration for the reaction pathway on ZrO<sub>2</sub> catalyst surface is still in the early stages, and several fundamental mechanisms remain unclear to hinder further development of DMC reaction. This study employs theoretical calculations to scrutinize the photothermal catalytic mechanism on tetragonal ZrO<sub>2</sub>(101) and Vo-ZrO<sub>2</sub>(101) surfaces from the perspective of CH<sub>3</sub>OH dissociation. Under illumination conditions, CH<sub>3</sub>OH is oxidized via photogenerated holes on the ZrO<sub>2</sub> surface, generating *CH<sub>2</sub>OH radicals. These radicals subsequently couple with *CO<sub>2</sub> to form the reaction intermediate *CH<sub>3</sub>OCOO, revealing a new photothermal catalytic reaction mechanism. The oxygen vacancies reduce the bandgap of ZrO<sub>2</sub>, enhancing its visible light responsiveness to promote CO<sub>2</sub> activation, and more importantly lower the energy barrier of the rate-determining step (215.5 kJ/mol vs. 188.9 kJ/mol), thereby facilitating the DMC synthesis. Furthermore, as guided by theoretical prediction, our experimental results demonstrate that ZrO<sub>2</sub> catalyst with abundant oxygen vacancies can achieve the higher DMC yield of 3.87 mmol·g<sup>−1</sup>. Under photothermal conditions, the DMC yield can be further elevated to 4.26 mmol·g<sup>−1</sup>. This work provides new theoretical insights into the DMC synthesis mechanism from CO<sub>2</sub> and CH<sub>3</sub>OH.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"469 ","pages":"Article 116582"},"PeriodicalIF":4.1,"publicationDate":"2025-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144279614","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}
引用次数: 0
Small-sized Au nanocage@Carbon quantum dots nanoprobe with high-efficiency imaging labeling and photothermal therapy 小型Au nanocage@Carbon量子点纳米探针,具有高效成像标记和光热治疗
IF 4.1 3区 化学
Journal of Photochemistry and Photobiology A-chemistry Pub Date : 2025-06-13 DOI: 10.1016/j.jphotochem.2025.116580
Naiqiang Yin , Chundong Liu , Yingying Wang , Zhaolei Ba , Jingwen Yang , Wenjun Liu , Jicui Zhang , Yan Li , Xiaoliang Xu , Lixin Zhu
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