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Depolymerization of PET and Polyamide 66 Wastes Using an Iron(III) Recoverable Lewis–Brønsted Aqueous System 铁(III)可回收Lewis-Brønsted水溶液体系解聚PET和聚酰胺66废弃物
IF 3.1 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-10-15 DOI: 10.1002/cplu.70267
Emanuele Vassallo, Marco Rollo, Lavinia Paletti, Gianluca Ciancaleoni, Elisa Martinelli

The accumulation of polyethylene terephthalate (PET) and polyamide 66 (PA66) in municipal and industrial waste streams represents a major challenge to global sustainability efforts. In this work, we report the development and optimization of a low-cost, iron-recoverable, and reconstitutable Lewis–Brønsted aqueous solution (LBAS) system for the selective depolymerization of post-consumer PET and PA66 wastes. The method employs a recyclable reaction medium and operates under mild conditions (150 °C, 2 h), achieving high monomer yields with excellent selectivity. The resulting terephthalic acid, adipic acid, and hexamethylenediammonium chloride were efficiently recovered and purified using straightforward separation techniques, whereas ethylene glycol was recovered as a stream suitable for purification by conventional industrial methods. A proof-of-concept experiment confirmed that PET and PA66 can also be depolymerized in the same medium, even though cross reactions between adipic acid and ethylene glycol prevent the quantitative monomer recovery. Therefore, mixed PET/PA66 feeds require prior separation to recover the individual monomers effectively. Overall, results demonstrate a scalable and environmentally benign approach for the chemical recycling of PET and PA66, contributing to a more sustainable plastic lifecycle and circular materials economy.

聚对苯二甲酸乙二醇酯(PET)和聚酰胺66 (PA66)在城市和工业废物流中的积累是对全球可持续发展努力的重大挑战。在这项工作中,我们报道了一种低成本、铁可回收、可重构的Lewis-Brønsted水溶液(LBAS)体系的开发和优化,该体系用于消费后PET和PA66废物的选择性解聚。该方法采用可循环的反应介质,在温和的条件下(150°C, 2 h)操作,单体收率高,选择性好。所得到的对苯二甲酸、己二酸和六亚甲基二氯化铵被有效地回收和使用直接分离技术纯化,而乙二醇被回收为适合用常规工业方法纯化的流。一项概念验证实验证实,即使己二酸和乙二醇之间的交叉反应阻止了定量单体回收,PET和PA66也可以在相同的介质中解聚。因此,混合PET/PA66进料需要事先分离以有效地回收单个单体。总体而言,研究结果表明,PET和PA66的化学回收是一种可扩展且环保的方法,有助于实现更可持续的塑料生命周期和循环材料经济。
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引用次数: 0
From Oxidative to Reductive Stress: Metal-Dependent Mechanisms of Cancer Cell Death in Troxerutin Complexes 从氧化到还原应激:曲克鲁汀复合物中癌细胞死亡的金属依赖机制。
IF 3.1 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-10-13 DOI: 10.1002/cplu.70262
A. Velásquez Bravo, A. B. Actis Dato, L. G. Naso, E. G. Ferrer, P. A. M. Williams

Flavonoid–oxidovanadium(IV) (VO) complexes have been widely investigated as anticancer agents because of their ability to induce oxidative stress in tumor cells. In contrast, Zn complexes with ligands capable of reducing intracellular reactive oxygen species (ROS) may exert antitumor effects through a reductive-stress mechanism. Herein, we report the synthesis and characterization of a Zn–troxerutin complex, its interaction with bovine serum albumin (BSA), and its anticancer activity. This study aims to correlate the chemical and biological properties of the complex after replacing a redox-active metal ion with a redox-inactive one. The Zn–troxerutin complex exhibited the same coordination mode and 1:1 metal-to-ligand stoichiometry as the VO analog. It showed dose-dependent antiproliferative activity at higher concentrations in A549, MDA-MB-231, and HCT-116 cancer cells, while reducing intracellular ROS. In HCT-116 cells, reductive stress was associated with increased glutathione (GSH) levels and mitochondrial membrane depolarization. The complex displayed greater anticancer efficacy than free troxerutin and selectivity toward cancer cells over normal HEK293 cells. BSA binding studies yielded positive ΔH and ΔS values, indicating that hydrophobic interactions drive complex formation, with binding constants within the optimal range for drug transport. These findings highlight Zn–troxerutin as a promising anticancer agent acting through reductive-stress pathways.

类黄酮-氧化钒(IV) (VO)配合物由于其在肿瘤细胞中诱导氧化应激的能力而被广泛研究作为抗癌药物。相比之下,具有能够减少细胞内活性氧(ROS)的配体的锌配合物可能通过还原性应激机制发挥抗肿瘤作用。在此,我们报道了锌-troxerutin复合物的合成和表征,它与牛血清白蛋白(BSA)的相互作用以及它的抗癌活性。本研究的目的是在用氧化还原活性金属离子取代氧化还原活性金属离子后,将配合物的化学和生物学特性联系起来。锌-troxerutin配合物表现出与VO类似物相同的配位模式和1:1的金属-配体化学计量。它在A549、MDA-MB-231和HCT-116癌细胞中显示出剂量依赖性的抗增殖活性,同时降低细胞内ROS。在HCT-116细胞中,还原性应激与谷胱甘肽(GSH)水平升高和线粒体膜去极化有关。该复合物显示出比游离曲鲁蛋白更强的抗癌功效,并且比正常HEK293细胞对癌细胞有更强的选择性。BSA结合研究得到了正的ΔH和ΔS值,表明疏水相互作用驱动复合物的形成,结合常数在药物运输的最佳范围内。这些发现突出了锌-troxerutin作为一种有前途的抗癌剂通过还原性应激途径发挥作用。
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引用次数: 0
On the Dynamics of Noncovalent Interactions Modulating Passive Diffusion of Cisplatin Across a Human Breast Cancer Cell Membrane: An amIGM + GLED View 非共价相互作用调节顺铂在人乳腺癌细胞膜上被动扩散的动力学:amIGM + GLED观点。
IF 3.1 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-10-13 DOI: 10.1002/cplu.70258
Costantino Zazza, Daniele Belletto, Stefano Scoditti, Nico Sanna, Stefano Borocci, Emilia Sicilia

Passive permeation across biological membranes is governed by a delicate balance of transient noncovalent interactions that are difficult to resolve experimentally or through conventional molecular dynamics (MD) analyses alone. Here, we present a perspective on the integration of the averaged modified independent gradient model (amIGM) based on promolecular density approximation and the graphic representation of the local electron energy density (GLED) with classical MD simulations to investigate the passive translocation of the cisplatin (cisPt) anticancer drug across a model membrane representative of the lipid composition of breast cancer cells. This multiscale framework combines atomistic sampling with real-space descriptors, enabling the dynamic characterization of hydrogen bonding, dispersion forces, steric effects, and local electronic stabilization trends along the permeation pathway. As a proof of concept, we analyze the supramolecular nanosolvation environment of cisPt at finite temperature in two representative states: bulk aqueous solution and membrane center, corresponding to the maximum of the potential of mean force (+16 kcal mol−1). The combined amIGM/GLED approach reveals how the nature and spatial distribution of drug–water interactions evolve in response to the local membrane environment, providing mechanistic insight into the electronic and supramolecular factors that shape the free-energy landscape of passive permeation.

通过生物膜的被动渗透是由瞬态非共价相互作用的微妙平衡控制的,这些相互作用很难通过实验或传统的分子动力学(MD)分析单独解决。在这里,我们提出了基于前分子密度近似的平均修正独立梯度模型(amIGM)和局部电子能量密度(GLED)的图形表示与经典MD模拟的整合的观点,以研究顺铂(cisPt)抗癌药物在代表乳腺癌细胞脂质组成的模型膜上的被动易位。这种多尺度框架结合了原子采样和实空间描述符,能够动态表征氢键、色散力、空间效应和渗透路径上的局部电子稳定趋势。为了证明这一概念,我们分析了在有限温度下cisPt的超分子纳米溶剂化环境,在两种具有代表性的状态下:大块水溶液和膜中心,对应于平均力势的最大值(+16 kcal mol-1)。结合amIGM/GLED方法揭示了药物-水相互作用的性质和空间分布如何随着局部膜环境的变化而演变,为形成被动渗透的自由能景观的电子和超分子因素提供了机制见解。
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引用次数: 0
Charge-Transfer Complexes of 3a,6a-Diaza-1,4-Diphosphapentalenes With the Organic π-Acceptor 2,3-Dicyanopyrazine and Its Derivatives 3a,6a-二氮杂-1,4-二磷五烯与有机π受体2,3-二氰吡嗪及其衍生物的电荷转移配合物。
IF 3.1 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-10-13 DOI: 10.1002/cplu.70270
Natalia Zolotareva, Matvey Grishin, Vyacheslav Sushev, Roman Rumyantcev, Georgy Fukin, Andrey Luk’yanov, Vlad Travkin, Artem Nazarov, Alexander Kornev

2,3-Dicyanopyrazine (DCNP) was first utilized as a π-acceptor to form charge-transfer complexes with strong π-donors, 3a,6a-diaza-1,4-diphosphapentalenes (RR’DDP), bearing peripheral methyl and annelated cyclohexyl substituents. The donor and acceptor molecules form mixed D–A–D–A stacks irrespective of the component ratio. The study of electron density topology indicated that each DCNP molecule accepts 0.22–0.24 electron charges in the crystal. The intermolecular interaction energy between donor and acceptor molecules ranges from 3.8 to 5.0 kcal/mol. An evaluation of the dark conductivity of the (cHexDDP•DCNP) sample showed an increase in current by ~5 orders of magnitude upon raising the temperature from 233 to 283 K. When RR’DDP interacts with acenaphthene- and cyclohexane-annelated 2,3-dicyanopyrazines, complexation is observed in solution, but CTC crystals do not form.

2,3-二氰吡嗪(DCNP)首次作为π受体与强π给体3a,6a-二氮杂-1,4-二磷五烯(RR'DDP)形成电荷转移配合物,并带有外围甲基和环己基取代基。无论组分比如何,供体和受体分子形成混合的D-A-D-A堆叠。电子密度拓扑研究表明,每个DCNP分子在晶体中接受0.22-0.24个电子电荷。供体和受体分子之间的分子间相互作用能在3.8 ~ 5.0 kcal/mol之间。对(cHexDDP•DCNP)样品的暗电导率的评估表明,当温度从233 K升高到283 K时,电流增加了约5个数量级。当RR'DDP与苊和环己烷的2,3-二氰吡嗪相互作用时,在溶液中观察到络合,但不形成CTC晶体。
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引用次数: 0
Chemical Upcycling of Poly(Lactic Acid) Waste Into Lactyl-Based Diols for the Synthesis of New Polyesters 聚乳酸废弃物化学升级回收成乳酸基二醇用于合成新型聚酯。
IF 3.1 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-10-11 DOI: 10.1002/cplu.70261
Federica Santulli, Andrea Annunziata, Pasquale D’Angelo, Marina Lamberti, Leonardo Marchese, Daniela Pappalardo, Mina Mazzeo

The development of efficient catalytic strategies for the chemical recycling and upcycling of poly(lactic acid) (PLA) is of great importance for advancing sustainable polymer technologies and promoting a circular plastics economy. Herein, we describe the selective alcoholysis of PLA promoted by a commercial titanium alkoxide and a phenoxy-imine pyridine zinc complex using various diols, leading to the formation of novel lactyl-based intermediates that were employed in subsequent polycondensation reactions with dicarboxylic acids. Alcoholysis reaction of PLA in the presence of ethylene glycol, 1,4-butanediol, cis-2-butene-1,4-diol and 3-allyloxy-1,2-propanediol afforded novel lactyl-containing diols, which were successfully reacted with adipic acid to produce a series of novel copolyesters. Structural characterization by one- and two-dimensional NMR spectroscopy confirmed the effective incorporation of lactyl units into the polymer backbones. Thermal analyses revealed that the introduction of lactyl moieties influences the crystallinity and thermal behavior of the resulting materials, generally leading to amorphous polymers. This approach demonstrates a straightforward and versatile route for the valorization of PLA waste into novel functional building blocks for the synthesis of potentially biodegradable polyesters with a variety of chemical features.

开发高效的聚乳酸(PLA)化学回收和升级利用催化策略对推进可持续聚合物技术和促进循环塑料经济具有重要意义。在本文中,我们描述了PLA的选择性醇解,由商业醇钛和苯氧亚胺吡啶锌配合物使用各种二醇促进,导致形成新的基于丙基的中间体,用于随后与二羧酸的缩聚反应。PLA在乙二醇、1,4-丁二醇、顺式-2-丁烯-1,4-二醇和3-烯丙氧基-1,2-丙二醇存在下的醇解反应得到了新型的含丙二醇,并成功地与己二酸反应生成了一系列新型共聚酯。通过一维和二维核磁共振波谱的结构表征证实了丙基单元有效地结合到聚合物骨架中。热分析表明,引入丙基基团会影响所得材料的结晶度和热行为,通常会导致非晶态聚合物。这种方法展示了一种简单而通用的途径,可以将聚乳酸废物转化为新的功能构建块,用于合成具有多种化学特征的潜在可生物降解聚酯。
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引用次数: 0
WO3/SnO2 n–n Heterojunction Photoanode for Clean Selective Photochemical Preparation of Benzaldehyde WO3/SnO2 n-n异质结光阳极清洁选择性光化学制备苯甲醛。
IF 3.1 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-10-11 DOI: 10.1002/cplu.70266
Jie Wang, Menggai Jia, Yuning Jia, Beibei Hu, Zhongqiu Li

Benzaldehyde is a vital intermediate for the synthesis of pharmaceuticals and agrochemicals. Traditional chemical synthesis methods are costly and cause environmental pollution. Therefore, developing novel green synthesis approaches is growing increasingly important. A photoelectrochemical (PEC) system was constructed using a WO3/SnO2 n–n heterojunction photoanode, with N-hydroxysuccinimide (NHS) acting as a selective hydrogen-atom-transfer mediator. The preparation parameters were optimized, and the material was characterized by SEM, TEM, XRD, XPS, and UV–vis diffuse reflectance spectroscopy. PEC properties and catalytic performance were evaluated. The optimized WO3/SnO2 exhibited extended light absorption and efficient charge separation. Under ambient conditions, the PEC system delivered 98% yield and 100% selectivity for benzaldehyde without using hazardous oxidants or causing substrate overoxidation. This work provides a green and efficient approach for benzaldehyde synthesis, offering theoretical and technical support for the PEC production of high-value fine chemicals and pharmaceutical intermediates.

苯甲醛是合成药品和农用化学品的重要中间体。传统的化学合成方法成本高且污染环境。因此,开发新的绿色合成方法变得越来越重要。采用WO3/SnO2 n-n异质结光阳极,n-羟基琥珀酰亚胺(NHS)作为选择性氢原子转移介质,构建了一种光电化学(PEC)体系。对制备工艺进行了优化,并用SEM、TEM、XRD、XPS和UV-vis漫反射光谱对材料进行了表征。对PEC的性能和催化性能进行了评价。优化后的WO3/SnO2具有较强的光吸收和高效的电荷分离性能。在环境条件下,PEC系统在不使用有害氧化剂或导致底物过度氧化的情况下,苯甲醛的收率为98%,选择性为100%。本研究为苯甲醛的绿色高效合成提供了一条途径,为高价值精细化学品和医药中间体的PEC生产提供了理论和技术支持。
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引用次数: 0
Valorization of Tectona grandis Leaf Waste Into Cellulose Nanocrystals, Nanofibers, and S/N-Doped Carbon Dots 大构造叶废料转化为纤维素纳米晶体、纳米纤维和S/ n掺杂碳点的研究。
IF 3.1 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-10-07 DOI: 10.1002/cplu.70259
Shiva Singh, Rohan Patgiri, Keshav Dev, Shakshi Bhardwaj, Pradip K. Maji

This study presents an integrated, waste-based route to produce chemically purified cellulose (CPC), cellulose nanofibers (CNF), cellulose nanocrystals (CNCs), and carbon dots (CDs) from Tectona grandis (teak) leaves. CPC was obtained by sequential dewaxing, chlorite bleaching, sulfite treatment, and alkaline extraction. CNFs were prepared by high-shear processing and sonication, while CNCs were produced by controlled sulfuric-acid hydrolysis. CDs, including sulfur- and nitrogen-doped variants, were synthesized via hydrothermal carbonization of leaf powder. Materials were characterized by proximate/ultimate (elemental) analysis, Fourier transform infrared spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), field-emission scanning electron microscopy (FESEM), atomic force microscopy, UV–vis/fluorescence spectroscopy, dynamic light scattering/zeta potential (ζ), and thermogravimetric analysis (TGA). Proximate/ultimate analysis indicates the leaves are a suitable feedstock (C ≈ 40.42 wt%, holocellulose ≈ 42.19 wt%, α-cellulose ≈ 18.18 wt%). XRD analysis yields a CNC crystallinity index of ≈63.19%. Microscopy confirms rod-like CNC morphology and nanoscale CDs. TGA shows thermal behavior consistent with a stable cellulose fraction, and preliminary antibacterial testing (Escherichia coli) was performed using the pour-plate method. The presented water-based procedures convert a combustible forest residue into value-added nanomaterials.

本研究提出了一种综合的、基于废物的途径,从柚木叶中生产化学纯化纤维素(CPC)、纤维素纳米纤维(CNF)、纤维素纳米晶体(cnc)和碳点(CDs)。经脱蜡、绿泥石漂白、亚硫酸盐处理、碱性萃取等工艺处理后,得到了CPC。CNFs是通过高剪切加工和超声制备的,而CNFs是通过控制硫酸水解制备的。以叶粉为原料,通过水热炭化法制备了硫掺杂和氮掺杂的CDs。对材料进行了近似/终极(元素)分析、傅里叶变换红外光谱、x射线衍射(XRD)、x射线光电子能谱(XPS)、透射电子显微镜(TEM)、场发射扫描电子显微镜(FESEM)、原子力显微镜、紫外可见/荧光光谱、动态光散射/ ζ电位(ζ)和热重分析(TGA)。近似/最终分析表明,叶片是合适的原料(C≈40.42 wt%,全新纤维素≈42.19 wt%, α-纤维素≈18.18 wt%)。XRD分析得出CNC结晶度指数为≈63.19%。显微镜检查证实了棒状CNC形态和纳米级cd。TGA显示其热行为与稳定的纤维素组分一致,并使用倾板法进行了初步的抗菌测试(大肠杆菌)。提出的水基程序将可燃森林残渣转化为增值纳米材料。
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引用次数: 0
Medium-Entropy NiFeMnCu Catalysts Enhance Aeration-Free Electrochemical Advanced Oxidation 中熵NiFeMnCu催化剂促进无曝气电化学高级氧化
IF 3.1 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-10-05 DOI: 10.1002/cplu.70260
Shuo Wang, Gaowei Zhang, Xiaofang Zheng, Bin Liao, Liu Lin, Zemin Sun

Advanced oxidation processes are among the mainstream and high-efficiency technologies for treating pharmaceutically active compounds and other water pollutants. However, most current electro-Fenton (EF) processes still rely on the use of Fe2+ and oxidizing agents, and the secondary pollution problem caused by metal ion leaching resulting therefrom has not yet been effectively addressed. Herein, we report a dual-system four-electrode EF cell that requires no addition of chemical reagents. The system employs a 300-nm-thick NiFeMnCu (NFMC) thin film, which not only functions as an OER collector for oxygen generation from both Anode I and Anode II, but also serves as a working electrode with a two-electron pathway to produce H2O2 through the electrochemical reduction of O2 at Cathode I. Furthermore, by integrating the Cathode II, NFMC cathode for the second-step sequential electrocatalytic reaction, the generation of H2O2 and its conversion to ·OH can be achieved. This catalytic system can effectively avoid problems such as metal sludge accumulation. When cefadroxil is used as the target pollutant, its removal can be completed within 30 min. Owing to the adoption of low-cost, durable, and scalable electrode materials, this process possesses high feasibility for practical application.

高级氧化工艺是处理药物活性化合物和其他水污染物的主流和高效技术之一。然而,目前大多数电fenton (electro-Fenton, EF)工艺仍然依赖于Fe2+和氧化剂的使用,其导致的金属离子浸出造成的二次污染问题尚未得到有效解决。本文报道了一种无需添加化学试剂的双系统四电极EF电池。该系统采用300 nm厚的NiFeMnCu (NFMC)薄膜,该薄膜不仅作为OER收集器从阳极I和阳极II生成氧气,而且作为双电子途径的工作电极,通过阴极I的电化学还原O2产生H2O2,并且通过将阴极II与NFMC阴极集成进行第二步顺序电催化反应,实现H2O2的生成并将其转化为·OH。该催化系统可有效避免金属污泥堆积等问题。以头孢地螺醇为目标污染物时,可在30min内完成去除。由于采用了低成本、耐用和可扩展的电极材料,该工艺具有很高的实际应用可行性。
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引用次数: 0
Triphenyl Imidazole-Phenothiazine Dual-Donor Organic Dyes With I-/I3 - Redox Couples for Highly Efficient Indoor Dye-Sensitized Photovoltaics. 具有I-/I3 -氧化还原对的三苯基咪唑-吩噻嗪双给体有机染料用于高效室内染料敏化光伏。
IF 3.1 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-10-01 DOI: 10.1002/cplu.70271
Andrew Simon George, Manne Naga Rajesh, Annu Annie George, Sruthi Meledath Meethal, Suraj Soman, Lingamallu Giribabu

Dye-sensitized solar cells are gaining recognition as a promising technology increasingly drawing the interest of a burgeoning array of IoT devices and wireless sensors, providing a solution to the escalating need for cordless power. We have chosen four organic sensitizers incorporating triphenyl imidazole and phenothiazine as double donors alongside a carboxylic acid as an anchoring group. Sensitizers have either benzothiadiazole (LG-P6 and LG-P8) or phenyl (LG-P5 and LG-P6) as an auxiliary acceptor, separated from the anchoring carboxylic acid group by an ethynyl bridge. The devices are fabricated using the I-/I3 - redox couple and evaluated under AM1.5G and indoor light conditions. The sensitizers having benzothiadiazole displayed efficiency of 5.98% and 2.81% under 1-sun conditions. Further, we have systematically evaluated device performance from 1000 to 100 lx WW CFL, WW LED, DL CFL, and DL LED light conditions. We observed efficiencies of 19.73% under 1000 lx WW CFL and 24.23% under 100 lx WW LED conditions using the LG-P6 sensitizer, which is one among the highest efficiencies reported without cosensitization to the best of our knowledge. Further, we adopted interfacial charge transfer studies using different perturbation techniques to explain the photovoltaic results.

染料敏化太阳能电池作为一项有前途的技术正在获得认可,越来越引起了新兴的物联网设备和无线传感器的兴趣,为不断升级的无线电源需求提供了解决方案。我们选择了四种有机增敏剂,包括三苯基咪唑和吩噻嗪作为双给体,羧酸作为锚定基团。敏化剂有苯并噻二唑(LG-P6和LG-P8)或苯基(LG-P5和LG-P6)作为辅助受体,通过乙基桥与锚定羧基分离。这些器件是使用I-/I3 -氧化还原偶对制造的,并在AM1.5G和室内光条件下进行了评估。含苯并噻二唑的增敏剂在1日光照条件下的效率分别为5.98%和2.81%。此外,我们系统地评估了从1000到100 lx WW CFL, WW LED, DL CFL和DL LED光条件下的器件性能。我们观察到,在1000 lx WW的CFL条件下,使用LG-P6敏化剂的效率为19.73%,在100 lx WW的LED条件下,使用LG-P6敏化剂的效率为24.23%,这是我们所知的在没有共敏化的情况下报道的最高效率之一。此外,我们采用了界面电荷转移研究,使用不同的微扰技术来解释光伏结果。
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引用次数: 0
Tunable Acidity of Sulfated Zr-Sn Mixed Oxides for Solvent-Free Sorbitol Dehydration to Isosorbide. 无溶剂山梨醇脱水制异山梨醇用硫酸锌锡混合氧化物的酸度可调。
IF 3.1 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-10-01 DOI: 10.1002/cplu.70273
Jay B Trivedi, Paresh H Rana

One of the most important processes in creating sustainable monomers for high-performance polymers is the catalytic dehydration of sorbitol obtained from biomass to isosorbide. This study investigated a series of sulfated ZrxSn1 - xO2 (x = 0.1-0.9) mixed oxides prepared by coprecipitation method for sorbitol dehydration under solvent-free conditions. Comprehensive evaluation of different characterization techniques, i.e., X-ray diffraction, Fourier transform infrared, transmission electron microscope, N2 physisorption, and NH3-TPD demonstrated that surface acidity, textural characteristics, and catalytic activity were greatly affected by catalyst composition. Catalyst with intermediate Zr content (0.4-0.6) had an ideal balance of weak, medium, and strong Brønsted acid sites, which resulted in complete conversion of sorbitol and higher isosorbide selectivity. 100% sorbitol conversion and 87% isosorbide selectivity were achieved with sulfated (S)-Zr0.5Sn0.5O2 at 220 °C within 3 h, exceeding many reported heterogeneous solid acids catalyst. A minor loss in catalyst activity was observed after four cycles, showing its potential for long-term isosorbide production.

在创造高性能聚合物可持续单体的最重要的过程之一是从生物质中获得的山梨醇催化脱水成异山梨醇酯。在无溶剂条件下,采用共沉淀法制备了一系列硫酸化ZrxSn1 - xO2 (x = 0.1 ~ 0.9)混合氧化物,用于山梨醇脱水。通过x射线衍射、傅里叶变换红外、透射电镜、N2物理吸附、NH3-TPD等不同表征手段的综合评价表明,催化剂组成对催化剂的表面酸度、结构特征和催化活性有较大影响。中等Zr含量(0.4 ~ 0.6)的催化剂具有较理想的弱、中、强Brønsted酸位平衡,可实现山梨醇的完全转化和较高的异山梨醇选择性。在220°C的条件下,硫酸钠(S)-Zr0.5Sn0.5O2在3 h内实现了100%的山梨醇转化率和87%的异山梨醇选择性,超过了许多报道的非均相固体酸催化剂。在四个循环后观察到催化剂活性的轻微损失,表明其长期生产异山梨酯的潜力。
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引用次数: 0
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