Journal of Photochemistry and Photobiology A-chemistry最新文献_第7页

Photo-Fenton dye degradation by BiOCl/Bi[Fe(CN)6]·4H2O prepared by mechanical milling 机械磨法制备BiOCl/Bi[Fe(CN)6]·4H2O降解光fenton染料

IF 4.7 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2026-01-08 DOI: 10.1016/j.jphotochem.2026.117029

Pongsaton Amornpitoksuk , Sumetha Suwanboon

In this study, BiOCl/Bi[Fe(CN)₆]·4H₂O composites were synthesized by ball-milling using Bi(NO₃)₃·5H₂O, KCl, and K₃[Fe(CN)₆] as precursor materials. The BiOCl/Bi[Fe(CN)₆]·4H₂O ratio of the composites decreased with decreasing KCl content. In the presence of hydrogen peroxide (H₂O₂), the degradation of rhodamine B (RhB) by the prepared catalysts was enhanced by visible-light irradiation, confirming their photo-Fenton properties. The degradation efficiency of RhB increased with increasing Bi[Fe(CN)₆]·4H₂O content in the composite. Compared with pure BiOCl and Bi[Fe(CN)₆]·4H₂O, the composite catalyst demonstrated a higher RhB degradation rate, which was ascribed to the efficient electron transfer from the conduction band of Bi[Fe(CN)₆]·4H₂O to that of BiOCl. The reactive species involved in the degradation process were investigated through trapping experiments and the results showed that hydroxyl radicals (^•OH) were the dominant active species, while superoxide anion radicals (^•O₂⁻) played a minor role. The degradation pathway of RhB was examined by introducing reaction samples collected at different reaction times into a mass spectrometer. The results indicated that, during the photo-Fenton process, RhB molecules were progressively decomposed into smaller intermediates and final products.

本研究以Bi(NO3)3·5H2O、KCl和K3[Fe(CN)6]为前驱体材料，采用球磨法制备了BiOCl/Bi[Fe(CN)6]·4H2O复合材料。随着KCl含量的降低，复合材料的BiOCl/Bi[Fe(CN)6]·4H2O比值减小。在过氧化氢（H2O2）存在下，可见光照射增强了催化剂对罗丹明B （RhB）的降解，证实了催化剂的光fenton性能。随着复合材料中Bi[Fe(CN)6]·4H2O含量的增加，RhB的降解效率提高。与纯BiOCl和Bi[Fe(CN)6]·4H2O相比，复合催化剂表现出更高的RhB降解率，这归因于Bi[Fe(CN)6]·4H2O导带向BiOCl导带的有效电子转移。通过捕集实验研究了参与降解过程的活性物质，结果表明，羟基自由基（•OH）是主要的活性物质，而超氧阴离子自由基（•O2−）起次要作用。通过将不同反应时间采集的反应样品引入质谱仪，考察了RhB的降解途径。结果表明，在光- fenton过程中，RhB分子逐渐分解为更小的中间体和最终产物。

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引用次数: 0

Molten salt assistance and heterostructure construction strategy for effectively enhancing H2O2 photosynthesis over modified g-C3N4/h-BN 改性g-C3N4/h-BN有效增强H2O2光合作用的熔盐辅助及异质结构构建策略

IF 4.7 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2026-01-07 DOI: 10.1016/j.jphotochem.2026.117032

Ruxue Ma , Yi Xiong , Fuyou Wang , Zhihao Chen , Xinxin Guan , Xiucheng Zheng

Graphitic carbon nitride (g-C₃N₄, CN) is promising in boosting H₂O₂ photosynthesis at present, but facing huge challenges due to the limitations of common CN (e.g. small specific surface area, low absorption coefficient, and fast recombination of photoinduced carriers). To overcome these drawbacks, herein, the novel type-II heterojunctions are successfully constructed from hexagonal boron nitride (h-BN, abbreviated as BN), melamine, and KCl with the one-pot calcination method. The molten salt effect of KCl and the hard template effect of BN optimize the interlayer spacing, porosity and structural uniformity of CN, thus optimizing the adsorption and photocatalytic properties. Moreover, the constructed heterostructure between BN and modified CN further favors the photoinduced charge transfer. Hence, the resulting composites afford exciting photocatalytic H₂O₂ synthesis performance. Particularly, catalyzed by MCN/BN-2, the H₂O₂ production rate is separately 1515.05 μmol g⁻¹ h⁻¹ and 3382.17 μmol g⁻¹ h⁻¹ irradiated by visible light and the simulated solar light, which are significantly higher than those over MCN, BN, and most of CN-based materials previously reported. The results of band potential analyses, relevant radical scavenging experiments, as well as electron paramagnetic resonance measurements verify that the photocatalytic H₂O₂ production over MCN/BN-2 by using 10 vol% EtOH solution is predominantly through the two-step single-electron oxygen reduction reaction (ORR) process. Also, the one-step two-electron ORR involves in H₂O₂ formation. This work not only develops a novel broad-spectrum responsive metal-free photocatalyst, but also enriches the deep understanding of the roles played by molten salt engineering and heterostructure in photocatalysis.

石墨化氮化碳（g-C3N4， CN）目前在促进H2O2光合作用方面有很大的前景，但由于普通CN的局限性（如比表面积小、吸收系数低、光诱导载流子重组快），面临着巨大的挑战。为了克服这些缺点，本文成功地以六方氮化硼（h-BN，简称BN）、三聚氰胺和氯化钾为原料，采用一锅烧结法构建了新型ii型异质结。KCl的熔盐效应和BN的硬模板效应优化了CN的层间间距、孔隙度和结构均匀性，从而优化了CN的吸附和光催化性能。此外，在BN和修饰CN之间构建的异质结构进一步有利于光诱导电荷转移。因此，所得到的复合材料具有令人兴奋的光催化H2O2合成性能。特别是在MCN/BN-2的催化下，在可见光和模拟太阳光照下，H2O2的产率分别为1515.05 μmol g−1 h−1和3382.17 μmol g−1 h−1，显著高于MCN、BN和大多数cn基材料的产率。带电位分析、自由基清除实验以及电子顺磁共振测量结果证实，使用10 vol% EtOH溶液在MCN/BN-2上光催化生成H2O2主要是通过两步单电子氧还原反应（ORR）过程。同样，一步双电子ORR也参与了H2O2的形成。这项工作不仅开发了一种新型的广谱反应性无金属光催化剂，而且丰富了对熔盐工程和异质结构在光催化中的作用的深刻认识。

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引用次数: 0

Exploring the substituents effect on fluorescence enhancement through ESIPT in 2-(2-Hydroxyphenyl)-4(3H)-quinazolinone (HPQ): A DFT and TD-DFT study 用ESIPT研究取代基对2-（2-羟基苯基）-4(3H)-喹唑啉酮（HPQ）荧光增强的影响：DFT和TD-DFT研究

IF 4.7 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2026-01-07 DOI: 10.1016/j.jphotochem.2026.117026

Sayed Zahid Nasim , Memona Nazeer , Muhammad Yar , Sidra Latif , Tayyaba Tariq , Mubeen Naz , Nadeem S. Sheikh

The excited state intramolecular proton transfer (ESIPT) dynamics in 2-(2-Hydroxyphenyl)-4(3H)-quinazolinone (HPQ) and its derivatives (HPQ-D) are systematically investigated using density functional theory and time-dependent DFT (TD-DFT) at the B3LYP/6-31G(d,p) level. The influence of electron-withdrawing (EDGs; CN, NO₂) and electron-donating (EWGs; OH, NH₂) groups at different ortho (X), meta (Y), and para (Z) positions of HPQ in its enol, transition state (TS), and keto form is investigated. Geometry optimizations, potential energy curves (PECs), UV–Vis spectra, and vibrational frequency analysis are employed to investigate the proton transfer from enol to keto and the characteristics of intramolecular hydrogen bonding. Among the studied HPQ-X, (CN) exhibited the lowest energy barrier (2.48 kcal mol⁻¹) for proton transfer, while unsubstituted HPQ showed a comparatively higher energy barrier (5.38 kcal mol⁻¹). Derivatives with electron-withdrawing groups exhibited red-shift fluorescence, reflecting the increased stabilization of the keto form in the excited state. Reduced density gradient analyses provide significant evidence of improved hydrogen bonding in HPQ both before and after substitution. The substitutions of both EDG and EWG types lower the HPQ HOMO-LUMO gap, which in turn weakens ICT and advances the ESIPT sequence. Changes in molecular polarity, which lead to the strengthening of intramolecular hydrogen bonding caused by substitution(s), are demonstrated by changes in the molecular electrostatic potential and dipole moment. These changes impact the ESIPT efficiency and the resultant fluorescence in the HPQ derivatives. The findings offer insight on how to customize the photophysics of a molecule through substitutions and further open avenues for designing fluorescent probes and optoelectronic devices based on ESIPT.

利用密度泛函理论和时间依赖DFT （TD-DFT）在B3LYP/6-31G（d,p）水平上系统地研究了2-（2-羟基苯基）-4(3H)-喹唑啉酮（HPQ）及其衍生物（HPQ- d）分子内激发态质子转移（ESIPT）动力学。研究了HPQ在烯醇态、过渡态和酮态中不同邻位(X)、间位(Y)和段(Z)位置的吸电子（EDGs、CN、NO2）和供电子（EWGs、OH、NH2）基团的影响。利用几何优化、势能曲线、紫外可见光谱和振动频率分析研究了烯醇到酮的质子转移和分子内氢键的特征。在所研究的HPQ- x中，（CN）表现出最低的质子转移能垒（2.48 kcal mol−1），而未取代HPQ表现出较高的质子转移能垒（5.38 kcal mol−1）。具有吸电子基团的衍生物表现出红移荧光，反映了在激发态下酮形式的稳定性增加。降低密度梯度分析提供了显著的证据，证明取代前后HPQ中的氢键都得到了改善。EDG和EWG的替换降低了HPQ HOMO-LUMO的差距，从而减弱了ICT，推进了ESIPT序列。分子极性的变化，导致取代(s)引起的分子内氢键的加强，可以通过分子静电势和偶极矩的变化来证明。这些变化影响了ESIPT的效率和HPQ衍生物中产生的荧光。这些发现为如何通过取代来定制分子的光物理特性提供了见解，并进一步为设计基于ESIPT的荧光探针和光电器件开辟了道路。

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引用次数: 0

AIE-active BODIPY sensors for high-sensitivity and selective Cu2+ detection in environmental and biological applications AIE-active BODIPY传感器，用于环境和生物应用中的高灵敏度和选择性Cu2+检测

IF 4.7 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2026-01-06 DOI: 10.1016/j.jphotochem.2026.117027

Peraya Phattrapornpisit , Pornthip Piyanuch , Pitchaya Amornkittithaworn , Jirapat Santatiwongchai , Sarawoot Impeng , Suttipong Wannapaiboon , Kantapat Chansaenpak , Anyanee Kamkeaw

Two new aggregate-based BODIPY derivatives, MS1 and MS2, were designed and synthesized to specifically detect Cu²⁺. Their sensing capabilities for Cu²⁺ are affected by the OH group attached to the benzene ring of the azo-benzene ligand. These characteristics display fluorescence quenching through aggregation-induced emission (AIE) phenomenon (MS1) and ratiometric fluorescence sensing (MS2) when complexed with Cu²⁺, depending on the number of hydroxyl groups attached to the benzene ring. X-ray absorption spectroscopy (XAS) probed at Cu K-edge revealed the complexation structures of MS1 and MS2 with Cu²⁺ during the sensing process. These sensors exhibit high sensitivity toward Cu²⁺ with a low limit of detection at the ppb level in both colorimetric and fluorogenic methods, which is significantly lower than the limits recommended by the WHO and U.S. EPA guidelines for drinking water. These sensors also exhibited excellent selectivity for Cu²⁺ over relevant competing metal ions in an aqueous system. Moreover, the sensor was successfully applied in fluorometric screening for the detection of Cu²⁺ in real water and soil samples, serving as a visual tool, and for imaging in living cells.

设计并合成了两个新的基于聚合体的BODIPY衍生物MS1和MS2，用于特异检测Cu2+。偶氮苯配体苯环上的羟基影响了它们对Cu2+的感应能力。当与Cu2+络合时，根据苯环上羟基的数量，通过聚集诱导发射（AIE）现象（MS1）和比例荧光感应（MS2）表现出荧光猝灭。x射线吸收光谱（XAS）在Cu - k边缘探测，揭示了MS1和MS2在传感过程中与Cu2+的络合结构。这些传感器对Cu2+具有高灵敏度，比色法和荧光法在ppb水平上的检测限低，明显低于世界卫生组织和美国环保署饮用水指南建议的限值。这些传感器在水体系中对Cu2+的选择性也优于相关的竞争金属离子。此外，该传感器已成功应用于实际水和土壤样品中Cu2+的荧光筛选检测，作为视觉工具，并在活细胞中成像。

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引用次数: 0

Tiny CuO/CeO2 modified bovine serum albumin with oxidase-like activity for reliable recognition of ascorbic acid and S2− in food 微量CuO/CeO2修饰的牛血清白蛋白具有类似氧化酶的活性，可可靠地识别食物中的抗坏血酸和S2−

IF 4.7 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2026-01-06 DOI: 10.1016/j.jphotochem.2026.117028

Huitian Zhi , Lingwei Bu , Ruhui Shang, Xujie Wang, Yingchao Yang, Wanyu Zhang, Zhengquan Yan, Lei Hu

Food health and safety is one of the hottest topics to affect human life nowadays. To reliably detect toxic S²⁻ and to normalize bioactive ascorbic acid (AA), a kind of tiny CuO/CeO₂ modified bovine serum albumin (CuO/CeO₂@BSA) was prepared under microwave-assisted conditions. Not only did the modification of BSA to CuO/CeO₂ nanospheres endow CuO/CeO₂@BSA with high stability and an average mesoporous pore of 3.88 nm, it exhibited outstanding oxidase-like activity to catalyze the oxidization of 3,3′,5,5′-tetramethyl benzidine (TMB) with V_max/K_m of 0.15 mM/5.96 × 10⁻⁸ M·s⁻¹. The presence of trace S²⁻ or AA could exclusively deteriorate the characteristic UV–vis absorbance intensity at 652 nm (A₆₅₂) of CuO/CeO₂@BSA-TMB with obvious hypochromic effect from dark blue to light blue. Under the optimal oxidase-mimic conditions, CuO/CeO₂@BSA-TMB was applied for potable UV–vis spectral/smartphones-assisted red-green-blue (RGB) monitoring of S²⁻ or AA in complex agricultural products with detection limits as low as 9.2 × 10⁻⁹/4.0 × 10⁻⁸ M or 6.1 × 10⁻⁸/7.2 × 10⁻⁸ M. The analysis accuracy was reliable from comparing their F and t values and the detection mechanisms were proposed. It will shed a potential for portable monitoring of analytes in food samples practically.

食品健康与安全是当今影响人类生活的热点问题之一。为了可靠地检测有毒的S2−和使生物活性抗坏血酸（AA）正常，在微波辅助条件下制备了一种微小的CuO/CeO2修饰牛血清白蛋白（CuO/CeO2@BSA）。BSA修饰后的CuO/CeO2纳米球不仅使CuO/CeO2@BSA具有较高的稳定性，平均介孔孔径为3.88 nm，而且在催化3,3 ',5,5 ' -四甲基联苯胺（TMB）氧化方面表现出优异的氧化酶样活性，Vmax/Km为0.15 mM/5.96 × 10−8 M·s−1。微量的S2−或AA的存在只会使CuO/CeO2@BSA-TMB在652nm处的特征紫外-可见吸收强度（A652）变差，并有明显的从深蓝色到浅蓝色的失色效应。在最佳氧化酶模拟条件下，将CuO/CeO2@BSA-TMB应用于复杂农产品的饮用水紫外-可见光谱/智能手机辅助红-绿-蓝（RGB）监测，检测限低至9.2 × 10−9/4.0 × 10−8 M或6.1 × 10−8/7.2 × 10−8 M，通过比较其F值和t值，分析精度可靠，并提出了检测机制。它将为食品样品中分析物的便携式监测提供实用的可能性。

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引用次数: 0

3-(Difluoromethyl)-7-(trifluoromethyl)pyrazolo[1,5-a]pyrimidines achieved by sequential formylation/difluorination reactions: Synthesis, optical properties, BSA bio-interactions, and molecular docking 顺序甲酰化/二氟化反应制备的3-（二氟甲基）-7-（三氟甲基）吡唑[1,5-a]嘧啶：合成、光学性质、BSA生物相互作用和分子对接

IF 4.7 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2026-01-04 DOI: 10.1016/j.jphotochem.2026.117024

Juliane N. Araújo , Felipe S. Stefanello , Érica O.T. Machado , Fábio M. Luz , Fabiane Gritzenco , Pablo A. Nogara , Marcos A.P. Martins , Nilo Zanatta , Victor Deflon , Bernardo A. Iglesias , Helio G. Bonacorso

This paper describes the synthesis and optical properties of a novel series of six examples of 5-aryl(heteroaryl)-3-difluoromethyl-7-(trifluoromethyl)-2-methylpyrazolo[1,5-a]pyrimidines (5), which is obtained through a sequential synthetic process. Initially, a Vilsmeier-Haack formylation reaction functionalized the 3-position of 5-aryl(heteroaryl)-7-(trifluoromethyl)-2-methylpyrazolo[1,5-a]pyrimidines (3), giving the 3-formyl derivatives (4) at yields of 60–91 %. Subsequently, the difluorination of aldehydes (4) using diethylaminosulfur trifluoride (DAST) converted the CHO function into the CHF₂ group, resulting in yields of 40–69 %. All new compounds 4 and 5 were fully characterized by ¹H, ¹³C, and ¹⁹F NMR, SC-XRD, HRMS, and UV–Vis spectroscopy. Additionally, TD-DFT calculations supported and rationalized the observed photophysical properties of series 4 and 5. Lastly, BSA-binding experiments and molecular docking evaluations showed the best interaction with site III of albumin was observed when 5-aryl was 4-BrC₆H₄ (5d).

本文介绍了通过序贯合成方法合成的6个新型5-芳基（杂芳基）-3-二氟甲基-7-（三氟甲基）-2-甲基吡唑[1,5-a]嘧啶(5)的合成及其光学性质。最初，Vilsmeier-Haack甲酰化反应将5-芳基（杂芳基）-7-（三氟甲基）-2-甲基吡唑[1,5-a]嘧啶(3)的3位功能化，得到3-甲酰基衍生物(4)，产率为60 - 91%。随后，使用二乙基氨基三氟化硫（DAST）对醛(4)进行二氟化反应，将CHO功能转化为CHF2基团，产率为40 - 69%。所有新化合物4和5都通过1H， 13C和19F NMR， SC-XRD， HRMS和UV-Vis光谱进行了充分的表征。此外，TD-DFT计算支持并合理化了系列4和系列5的观测光物理性质。最后，bsa结合实验和分子对接评价表明，当5-芳基为4-BrC6H4 （5d）时，与白蛋白III位点的相互作用最佳。

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引用次数: 0

Constructing photochromic cotton fabrics by thiol-Ene click chemistry: The enhancing effect of hydrogen bonding on comprehensive properties 巯基烯键合化学构造光致变色棉织物：氢键对综合性能的增强作用

IF 4.7 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2026-01-04 DOI: 10.1016/j.jphotochem.2026.117025

Chengwen Jin , Ruizhen Zhang , Pengjie Xie , Tao Chen

Spiropyran-based photochromic materials have attracted considerable attention in the textile field due to their exceptional reversible photochromic properties. Current spiropyran-modified fabrics still confront challenges regarding light-stimulus response rate, photofatigue resistance etc. In this study, a carbamate functional group capable of forming hydrogen bonds was introduced into the spiropyran molecule. Via thiol-ene click chemistry, cotton fabrics modified with 3-mercaptopropyltrimethoxysilane (MPTMS) were covalently bonded with the modified spiropyran, resulting in the preparation of SPMA-type photochromic cotton fabrics. Compared with SPA cotton fabrics without carbamate functional groups, the constructed SPMA cotton fabrics exhibited enhanced overall photochromic performance. The resulting SPMA cotton fabrics exhibited rapid coloration within 2 s under 365 nm UV irradiation and quick reversion to the initial colorless state upon UV removal. Furthermore, more than 85 % of the photochromic performance was retained even after 20 repeated UV/visible irradiation cycles. The enhanced performance originates from intermolecular hydrogen bonding between carbamate groups in SPMA, which stabilizes the open-ring merocyanine (MC) structure and promotes SP → MC isomerization, while concurrently improving photofatigue resistance. Benefiting from the outstanding photochromic reversibility, photofatigue resistance, and mechanical stability, the SPMA cotton fabric demonstrates promising application potential in UV protection, pattern switching, information encryption, and ink-free writing. This work provides a new strategy for the design and performance optimization of smart textile materials based on spiropyran photochromic systems.

螺吡喃基光致变色材料以其独特的可逆光致变色性能在纺织领域引起了广泛的关注。目前，螺吡喃改性织物在光刺激响应速率、抗光疲劳性能等方面仍面临挑战。在本研究中，在螺吡喃分子中引入了一个能够形成氢键的氨基甲酸酯官能团。通过巯基点击化学，将3-巯基丙基三甲氧基硅烷（MPTMS）改性棉织物与改性后的螺吡喃共价结合，制备了spma型光致变色棉织物。与不含氨基甲酸酯官能团的SPA棉织物相比，SPMA棉织物的整体光致变色性能有所提高。所得的SPMA棉织物在365 nm紫外线照射下，在2 s内快速着色，在紫外线去除后迅速恢复到初始无色状态。此外，超过85%的光致变色性能，即使经过20次重复的紫外/可见光照射循环仍保持不变。SPMA中氨基甲酸酯基团之间的分子间氢键稳定了开环merocyanine （MC）结构，促进了SP→MC异构化，同时提高了抗光疲劳性能。凭借优异的光致变色可逆性、抗光疲劳性和机械稳定性，SPMA棉织物在紫外线防护、图案切换、信息加密和无墨书写等方面具有广阔的应用前景。本研究为基于螺吡喃光致变色系统的智能纺织材料的设计和性能优化提供了一种新的策略。

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引用次数: 0

A fluorescent sensing system based on Fe-doped ZIF-8 for highly selective detection of glyphosate in cucumber and Sugarbeet 基于fe掺杂ZIF-8的高选择性检测黄瓜和甜菜中草甘膦的荧光传感系统

IF 4.7 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2026-01-02 DOI: 10.1016/j.jphotochem.2026.117023

Xiaoqian Liu , Pute Yang , Shangyu Hou , Rong Yang , Qin Zhou , Xiwei Wang

The widespread application of glyphosate has led to severe threats to both ecosystems and human health. Conventional detection technologies, which typically depend on sophisticated instruments and involve complex operational procedures, are characterized by low response efficiency. Addressing this challenge necessitates the development of novel detection methods that are simple to operate, highly sensitive, and yield reliable results. In this work, an Fe-doped ZIF-8 composite material (Fe@ZIF-8) was synthesized using a room-temperature precipitation method. To investigate the feasibility of Fe@ZIF-8 for glyphosate sensing, its structural stability and detection mechanism were verified through characterization by FTIR, XRD, SEM and XPS. It was verified that a stable coordination compound is formed between the Fe³⁺ sites in the studied material and the phosphonic acid and carboxyl functional groups present in the glyphosate molecule by density function theory (DFT) calculations.Through methodological investigation, it can be concluded that a strong linear correlation between the fluorescence difference (ΔF) and the natural logarithm of glyphosate concentration in the range of 0.05–3 mg/L. The regression equation was determined to be ΔF = 50.22 + 134.84ln (x + 0.85), with a correlation coefficient (R²) of 0.99386. The detection limit was calculated to be 0.022 mg/L, confirming the high sensitivity of this approach. Given its excellent reproducibility, water stability, and simple preparation, Fe@ZIF-8 presents a new and viable strategy for the detection of glyphosate in practical applications.

草甘膦的广泛使用对生态系统和人类健康都造成了严重威胁。传统的检测技术通常依赖于精密的仪器，涉及复杂的操作程序，其特点是响应效率低。为了应对这一挑战，需要开发操作简单、灵敏度高、结果可靠的新型检测方法。本文采用室温沉淀法合成了一种掺铁的ZIF-8复合材料（Fe@ZIF-8）。为了考察Fe@ZIF-8传感草甘膦的可行性，通过FTIR、XRD、SEM和XPS等表征手段验证了其结构稳定性和检测机理。通过密度泛函理论（DFT）计算验证了材料中的Fe3+位点与草甘膦分子中的膦酸和羧基官能团之间形成了稳定的配位化合物。通过方法学研究，可以得出荧光差（ΔF）与草甘膦浓度的自然对数在0.05 ~ 3 mg/L范围内具有很强的线性相关性。回归方程为ΔF = 50.22 + 134.84ln (x + 0.85)，相关系数（R2）为0.99386。方法的检出限为0.022 mg/L，具有较高的灵敏度。由于其优异的重现性、水稳定性和制备简单，Fe@ZIF-8在实际应用中为草甘膦的检测提供了一种新的可行策略。

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引用次数: 0

Mechanisms of halide oxidation to hypohalous acids on metal oxide photoanodes 金属氧化物光阳极上卤化物氧化成次卤酸的机理

IF 4.7 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2026-01-02 DOI: 10.1016/j.jphotochem.2026.117022

Hitoshi Kusama

The mechanisms underlying the photoelectrochemical oxidation of HX (X = Br and Cl) and H₂O to hypohalous acid (HOX) on Fe₂O₃, TiO₂, and BiVO₄ were investigated using density functional theory. We found five reaction pathways including two proton-coupled electron transfers (PCETs). Pathway 1, involving one HX and one H₂O molecules, proceeded as follows: HX adsorption, the first PCET, H₂O adsorption, and the second PCET. In pathways 2 and 3, instead of H₂O adsorption, a second HX was adsorbed, and the subsequent second PCET step generated X₂ species, which disproportionated with H₂O into HOX and HX. In pathways 4 and 5, two H₂O molecules oxidized to hydrogen peroxide, which oxidized HX to HOX and H₂O. The free-energy changes in the elementary steps of the oxidation mechanism indicated that the second (first) PCET required the highest energy input and was the rate-limiting step on Fe₂O₃ (TiO₂ and BiVO₄) regardless of pathway and HX reactant, whereas pathways 1 and 2 were the dominant paths on Fe₂O₃ and on TiO₂ and BiVO₄, respectively. Based on the computational results, the effects of using metal oxide as a photoanode on the in situ generation of X oxidative active species for mediating photoelectrochemical organic transformations are discussed.

利用密度泛函理论研究了HX （X = Br和Cl）和H2O在Fe2O3、TiO2和BiVO4上光电氧化生成次卤酸（HOX）的机理。我们发现了五种反应途径，包括两种质子耦合电子转移（PCETs）。途径1涉及一个HX和一个H2O分子，其过程如下：HX吸附，第一个PCET， H2O吸附，第二个PCET。在途径2和途径3中，不是H2O吸附，而是第二个HX被吸附，随后的第二个PCET步骤产生X2种，X2种与H2O歧化成HOX和HX。在途径4和5中，两个H2O分子被氧化为过氧化氢，过氧化氢又将HX氧化为HOX和H2O。氧化机制基本步骤的自由能变化表明，无论途径和HX反应物如何，第二（第一）PCET都需要最高的能量输入，并且是Fe2O3 （TiO2和BiVO4）的限速步骤，而途径1和途径2分别是Fe2O3和TiO2和BiVO4的主要途径。在计算结果的基础上，讨论了金属氧化物作为光阳极对X氧化活性物质原位生成的影响。

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引用次数: 0

IF 4.7 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2026-01-01

引用次数: 0