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Suppression of hydrogen-related defect in ZnWO4/HRP S-scheme heterojunction to enhance internal charge transfer in materials 抑制ZnWO4/HRP S-scheme异质结中氢相关缺陷增强材料内部电荷转移
IF 3.5 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-10-29 DOI: 10.1007/s11164-025-05755-6
Yalian Li, Jinxuan Han, Guozhu Li, Honggang Zhao, Yuhua Ma, Qingling Bai, Zhicheng Wang

In photocatalytic degradation of pollutants, hydrogen-related defects on the catalyst surface inhibit the generation of highly reactive superoxide radicals (·O2). Therefore, strategies to mitigate such defects are crucial for enhancing photocatalytic efficiency. To address this challenge, ZnWO4/hydrothermal red phosphorus (ZnWO4/HRP) S-scheme heterojunction photocatalysts were successfully prepared via a simple hydrothermal method, constructing a compact interfacial structure where rod-shaped ZnWO4 uniformly attaches to the HRP surface. Photocatalytic performance tests revealed that the composites exhibited excellent catalytic activity for rhodamine B (RhB) degradation, with a rate constant of 0.21 min−1 within 15 min-3.5 and 21 times higher than those of individual HRP and ZnWO4, respectively. Moreover, due to the robust chemical structure and strong interfacial bonding between ZnWO4 and HRP, the composite maintains high photocatalytic stability across multiple catalytic cycles. Mechanistic analysis demonstrates that the S-scheme heterojunction effectively suppresses the formation of hydrogen-related defects on the ZnWO4 surface, significantly reducing surface defect state density. This inhibition enhances photogenerated carrier separation, accelerates charge transfer, and facilitates the efficient generation of ·O2. By adopting a heterojunction strategy to address hydrogen-related defects, the catalyst’s visible-light absorption capacity, photoelectric conversion efficiency, and radical generation efficiency was enhanced, while carrier recombination was suppressed. These findings provide new insights for designing high-efficiency heterojunction photocatalysts and highlight their promising potential in photocatalytic removal of organic pollutants.

Graphical abstract

在光催化降解污染物的过程中,催化剂表面的氢相关缺陷抑制了高活性超氧自由基(·O2−)的产生。因此,减轻这些缺陷的策略对于提高光催化效率至关重要。为了解决这一难题,通过简单的水热法成功制备了ZnWO4/水热红磷(ZnWO4/HRP) s型异质结光催化剂,构建了紧凑的界面结构,使ZnWO4均匀地附着在HRP表面。光催化性能测试表明,复合材料对罗丹明B (RhB)的降解具有良好的催化活性,在15 min-3.5 min内的速率常数为0.21 min−1,比单独的HRP和ZnWO4分别高21倍。此外,由于坚固的化学结构和ZnWO4与HRP之间强大的界面键合,该复合材料在多个催化循环中保持较高的光催化稳定性。机理分析表明,s型异质结有效抑制了ZnWO4表面氢相关缺陷的形成,显著降低了表面缺陷态密度。这种抑制作用增强了光生载流子分离,加速了电荷转移,促进了·O2−的有效生成。通过采用异质结策略解决氢相关缺陷,提高了催化剂的可见光吸收能力、光电转换效率和自由基生成效率,抑制了载流子复合。这些发现为设计高效的异质结光催化剂提供了新的见解,并突出了其在光催化去除有机污染物方面的潜力。图形抽象
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引用次数: 0
Solar light-assisted photocatalytic degradation of organic pollutants using sustainable bio-fabricated NiO nanoparticles from almond peel extract 太阳能辅助光催化降解有机污染物的可持续生物合成纳米NiO杏仁皮提取物
IF 3.5 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-10-29 DOI: 10.1007/s11164-025-05792-1
Rinku Rana, Waseem Ahmad, Noha Al-Qasmi, Mohammad Shariq

This research focuses on the synthesis of NiO nanoparticles via a bio-fabrication method, where almond peel extract serves as both a stabilizing and capping agent. The effectiveness of these nanoparticles in the photocatalytic treatment of the organic pollutant was comprehensively evaluated, considering various influencing factors, including organic pollutant concentration, catalyst dosage, and pH. The structural, optical, morphological, and functional groups of the fabricated materials were examined by employing XRD, UV, SEM, and FTIR techniques. The fabricated nanoparticles exhibited an average crystallite size of 20.98 nm. The degradation potential of the fabricated materials was found to be decreased with increasing the initial pollutant concentration, while it improved with a higher catalyst dosage and increasing the solution pH during the photocatalysis. NiO nanoparticles demonstrated the greatest photocatalytic removal of brilliant green and amoxicillin after 120 min solar light exposure, reaching degradation efficiency of 79.13% and 43.05% for brilliant green and amoxicillin, respectively. The removal of amoxicillin follows pseudo-first-order kinetics with an R2 value of 0.89882, while the breakdown of the brilliant green follows a first-order reaction with an R2 value of 0.96426. This eco-friendly synthesis procedure reduces the environmental impact associated with the conventional chemical process by harnessing the renewable resources of almond peel, offering a sustainable combat against environmental degradation.

本研究的重点是通过生物制造方法合成NiO纳米颗粒,其中杏仁皮提取物作为稳定剂和封盖剂。综合考虑有机污染物浓度、催化剂用量、ph等多种影响因素,对纳米颗粒光催化处理有机污染物的效果进行了综合评价。采用XRD、UV、SEM、FTIR等技术对制备的材料进行了结构、光学、形态、官能团等表征。制备的纳米颗粒平均晶粒尺寸为20.98 nm。在光催化过程中,制备的材料的降解电位随初始污染物浓度的增加而降低,随催化剂用量的增加和溶液pH的增加而提高。在太阳光照120 min后,纳米NiO对绿光和阿莫西林的降解效率最高,分别达到79.13%和43.05%。阿莫西林的去除符合拟一阶动力学,R2值为0.89882,而绿光的分解符合一阶动力学,R2值为0.96426。这种生态友好的合成过程通过利用杏仁皮的可再生资源,减少了与传统化学过程相关的环境影响,为防止环境退化提供了可持续的斗争。
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引用次数: 0
Correction: Tetramethyl-dipropylene-triamine-modified triazine immobilized on silica-coated magnetic nanoparticles: an eco-friendly and reusable catalyst for the solvent-free synthesis of 2-amino-4H-chromene derivatives 四甲基-二丙烯-三胺修饰的三嗪固定化二氧化硅包覆磁性纳米颗粒:用于无溶剂合成2-氨基- 4h -铬衍生物的环保可重复使用催化剂
IF 3.5 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-10-28 DOI: 10.1007/s11164-025-05793-0
Noor Alhuda Basim Abd, Hashim Sheerali, Bashaer Jabar Hussein
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引用次数: 0
Synthesis and characterization of Fe3O4-β-cyclodextrin immobilized on graphene oxide nanosheets (Fe3O4-β-CD-GO): an efficient and convenient heterogeneous catalyst for the multi-component synthesis of 2-amino-3-cyano-4H-chromene derivatives in aqueous media 氧化石墨烯纳米片上固定化Fe3O4-β-环糊精(Fe3O4-β-CD-GO)的合成与表征:一种高效、便捷的多组分水相合成2-氨基-3-氰基- 4h -铬衍生物催化剂
IF 3.5 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-10-27 DOI: 10.1007/s11164-025-05791-2
Hussein Ali Qabel, Alalwan Dhurgham Hani Kadhim, Hussein Dhahir Ayyez Al-fatlawiy, Raed Muslim Mhaibes

The synthesis of bioactive chromene derivatives is of great significance due to their diverse pharmacological properties. In this study, a novel magnetically recoverable nanocatalyst, Fe3O4-β-cyclodextrin-graphene oxide (Fe3O4-β-CD-GO), was developed and thoroughly characterized using techniques such as Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Fourier-Transform Infrared Spectroscopy (FT-IR), X-ray Diffraction (XRD), Thermogravimetric Analysis (TGA), and Vibrating Sample Magnetometer (VSM), confirming its successful fabrication, stability, and magnetic properties. This heterogeneous catalyst was employed for the efficient and green synthesis of 2-amino-3-cyano-4H-chromenes in aqueous media at 80 °C, showing excellent yields up to 95% within short reaction times (10–60 min). Optimization studies highlighted the superior performance of water as a solvent, with catalyst loading (0.7 mol%) and temperature significantly influencing reaction efficiency. The catalyst demonstrated remarkable recyclability, maintaining high activity over at least eight cycles, facilitated by easy magnetic separation. A plausible reaction mechanism was proposed, involving activation of electrophiles and nucleophiles via hydrogen bonding and acid–base interactions. The method proved versatile, accommodating various aldehyde substrates with different electronic properties, and scalable for larger-scale synthesis. These findings underscore the catalyst’s potential for sustainable, cost-effective, and efficient organic transformations, advancing green chemistry protocols in pharmaceutical and material synthesis.

Graphical abstract

生物活性铬胺衍生物具有多种药理性质,因此其合成具有重要意义。在本研究中,开发了一种新型磁可回收纳米催化剂Fe3O4-β-环糊精-氧化石墨烯(Fe3O4-β-CD-GO),并利用扫描电镜(SEM)、透射电镜(TEM)、傅里叶变换红外光谱(FT-IR)、x射线衍射(XRD)、热重分析(TGA)和振动样品磁强计(VSM)等技术对其进行了全面表征,证实了其制备成功、稳定性和磁性能。该非均相催化剂用于在80°C的水介质中高效、绿色地合成2-氨基-3-氰基- 4h -铬,在短反应时间内(10-60 min),产率高达95%。优化研究强调了水作为溶剂的优越性能,催化剂负载(0.7 mol%)和温度对反应效率有显著影响。催化剂表现出显著的可回收性,在至少8个循环中保持高活性,易于磁分离。提出了一个合理的反应机制,包括通过氢键和酸碱相互作用激活亲电试剂和亲核试剂。该方法被证明是通用的,适用于具有不同电子性质的各种醛基,并且可扩展到更大规模的合成。这些发现强调了催化剂在可持续、低成本和高效有机转化方面的潜力,推动了药物和材料合成中的绿色化学协议。图形抽象
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引用次数: 0
Synthesis and adsorption capability of benzyl alcohol-based hyper-cross-linked resins for phenol removal in aqueous solution 苯甲醇基超交联树脂的合成及其对苯酚的吸附性能
IF 3.5 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-10-25 DOI: 10.1007/s11164-025-05789-w
Sitong Wang, Xiaoli Wu, Wenkai Chen, Yang Tan, Gui Chen, Fan Li, Shiqi Zhou, Meichun Wu

Benzyl alcohol (BOL), an aromatic compound bearing oxygen-containing functional groups, is capable of forming BOL-based hyper-cross-linked resin (BOL-HCPs) with chloromethylated polystyrene resins (CMPs) via a sequence of chemical reactions. A combination of characterization techniques, including BET, FT-IR, SEM-Mapping, XPS, XRD, contact angle measurement, and TGA, was confirmed the successful preparation of the adsorbent. Notably, the incorporation of BOL significantly increases both the specific surface area (SBET) and hydrophilicity of the adsorbent. BOL-HCPs, prepared by Friedel–Crafts alkylation and nucleophilic substitution reaction, exhibited excellent phenol removal capacity from aqueous solutions. The Langmuir isotherm model better describes the resin’s equilibrium adsorption, showing a max capacity of 275.2 mg/g at 298 K. Kinetic analysis reveals that the adsorption of pollutants reaches equilibrium rapidly within 90 min, which is consistent with the pseudo-first-order model. Owing to its favorable SBET, abundant micropores/mesopores, as well as hydrogen bonding interactions, the adsorbent enables highly efficient phenol adsorption. This work offers a new strategy for phenol removal from aqueous solutions.

Graphical Abstract

苄基醇(BOL)是一种含氧官能团的芳香族化合物,它能够与氯甲基化聚苯乙烯树脂(cmp)通过一系列化学反应形成基于BOL的超交联树脂(BOL- hcps)。结合BET、FT-IR、SEM-Mapping、XPS、XRD、接触角测量、TGA等表征技术,证实了吸附剂的成功制备。值得注意的是,BOL的加入显著增加了吸附剂的比表面积(SBET)和亲水性。通过Friedel-Crafts烷基化和亲核取代反应制备的BOL-HCPs具有优异的苯酚脱除能力。Langmuir等温线模型更好地描述了树脂的平衡吸附,在298 K下的最大吸附容量为275.2 mg/g。动力学分析表明,吸附污染物在90 min内迅速达到平衡,符合拟一阶模型。由于其良好的SBET,丰富的微孔/介孔,以及氢键相互作用,使得吸附剂能够高效吸附苯酚。这项工作为从水溶液中去除苯酚提供了一种新的策略。图形抽象
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引用次数: 0
Biosynthesis of MnO2 for MnO2@Ag–S–CH2–COOH: a novel catalyst for one-pot three-component synthesis of hydrazinyl thiazole derivatives, their anti-bacterial and anti-cancer study MnO2生物合成MnO2@Ag -S-CH2-COOH:一锅法合成三组分肼基噻唑衍生物的新型催化剂及其抑菌抗癌研究
IF 3.5 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-10-24 DOI: 10.1007/s11164-025-05787-y
Shankar P. Phulwale, Avinash A. Survase, Shivaji D. Waghmare, Akshay P. Gurav, Lalit D. Bhosale, Madanrao M. Patil, Dnyaneshwar S. Wankhede, Krishna Chaitanya Gunturu, Shankar P. Hangirgekar

This study outlines an easy, efficient and environmentally sustainable method for the green synthesis of manganese dioxide (MnO2) nanoparticles using an extract from Psidium guajava leaves. The catalytic activity of MnO2@Ag–S–CH2–COOH nanocatalyst was explored for the one-pot synthesis of hydrazinyl thiazole derivatives, utilizing a three-component reaction involving different aryl aldehydes, phenacyl bromides, and thiosemicarbazide. A number of techniques were used to characterize the MnO2@Ag–S–CH2–COOH nanocatalyst, field emission scanning electron microscopy (FE-SEM), Brunner–Emmett–Teller (BET), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HR-TEM), X-ray photoelectron spectroscopy (XPS), and energy-dispersive X-ray (EDX). The structures of each newly synthesized derivative of hydrazinyl thiazole have been confirmed via the use of nuclear magnetic resonance (1H and 13C NMR), fourier-transform infrared (FTIR) and high resolution mass spectrometry (HRMS). The MnO2@Ag–S–CH2–COOH nanocatalyst was readily extracted from the reactions with the use of an external magnet and could be reused five times without experiencing a substantial loss in efficacy. The synthesized compounds demonstrated promising results when assessed in vitro for their antimicrobial and anticancer activities. The anticancer efficacy of the synthesized hydrazinyl thiazole compounds were assessed in vitro against the MCF-7 human breast cancer cell line using the MTT assay. Among them, compounds 4a and 4e exhibited notable anticancer effects, with IC50 values of 82.30 ± 0.58 and 84.25 ± 0.28 μg/mL respectively.

这项研究概述了一种简单、高效和环境可持续的方法,利用番石榴叶提取物绿色合成二氧化锰纳米颗粒。考察了MnO2@Ag -S-CH2-COOH纳米催化剂在不同芳醛、苯酰溴和硫代氨基脲三组分反应中一锅合成肼基噻唑衍生物的催化活性。采用了多种技术对MnO2@Ag -S-CH2-COOH纳米催化剂进行表征,包括场发射扫描电镜(FE-SEM)、Brunner-Emmett-Teller (BET)、x射线衍射(XRD)、高分辨率透射电子显微镜(HR-TEM)、x射线光电子能谱(XPS)和能量色散x射线(EDX)。通过核磁共振(1H和13C NMR)、傅里叶变换红外(FTIR)和高分辨率质谱(HRMS)等手段对新合成的肼基噻唑衍生物的结构进行了确证。MnO2@Ag -S-CH2-COOH纳米催化剂很容易用外部磁铁从反应中提取,并且可以重复使用五次而不会有明显的效果损失。合成的化合物在体外抗菌和抗癌活性评估中显示出良好的结果。采用MTT法测定合成的肼基噻唑类化合物对MCF-7人乳腺癌细胞株的体外抗癌作用。其中化合物4a和4e具有显著的抗癌作用,IC50值分别为82.30±0.58和84.25±0.28 μg/mL。
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引用次数: 0
Preparation of morphology-controlled ZSM-5 zeolites adsorbent and Pt/ZSM-5 catalysts: toluene adsorption and catalytic oxidation performance 形貌可控的ZSM-5分子筛吸附剂及Pt/ZSM-5催化剂的制备:甲苯吸附及催化氧化性能
IF 3.5 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-10-24 DOI: 10.1007/s11164-025-05786-z
Weibing Deng, Rui Zhang, Wei Deng, Shuai Wang, Qiongyu Liu, Haoran Chang

A series of Pt-based catalysts supported on morphology-controlled ZSM-5 zeolites were synthesized and applied for toluene catalytic oxidation. The results demonstrated that the catalyst Pt supported on sheet-like ZSM-5 (Pt/S-ZSM) exhibited significantly higher activity than those supported on chain-like ZSM-5 (Pt/C-ZSM) and unmodified ZSM-5 (Pt/N-ZSM). The sheet-like morphology ZSM-5 zeolites exhibited a toluene saturation capacity of 65.17 mg·g−1, with breakthrough time and saturation adsorption increased by 2.4-fold and 1.4-fold, respectively, compared to unmodified N-ZSM-5. Notably, compared to 0.5wt% Pt/C-ZSM, the 0.5wt% Pt/S-ZSM catalyst exhibited a significantly lower apparent activation energy (11.63 kJ·mol−1), confirming the superior suitability of S-ZSM as a Pt support. This was further evidenced by its exceptional catalytic activity, achieving 90% toluene conversion (T90) at just 181℃. The Pt/S-ZSM showed well catalytic activity and structural stability during the toluene catalytic combustion, which reflected a promising catalyst for practical application.

合成了一系列以ZSM-5分子筛为载体的pt基催化剂,并将其应用于甲苯的催化氧化。结果表明,负载在片状ZSM-5 (Pt/S-ZSM)上的Pt催化剂的活性明显高于负载在链状ZSM-5 (Pt/C-ZSM)和未改性ZSM-5 (Pt/N-ZSM)上的Pt催化剂。片状ZSM-5分子筛的甲苯饱和容量为65.17 mg·g−1,突破时间和饱和吸附分别比未改性的N-ZSM-5增加2.4倍和1.4倍。值得注意的是,与0.5wt% Pt/C-ZSM相比,0.5wt% Pt/S-ZSM催化剂的表观活化能(11.63 kJ·mol−1)显著降低,证实了S-ZSM作为Pt载体的卓越适用性。其优异的催化活性进一步证明了这一点,在181℃下,甲苯转化率达到90% (T90)。Pt/S-ZSM在甲苯催化燃烧过程中表现出良好的催化活性和结构稳定性,是一种具有实际应用前景的催化剂。
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引用次数: 0
Enhanced adsorption capabilities of Salen-Co-MCM-41-bipy complex in Knoevenagel condensation as a versatile catalyst Salen-Co-MCM-41-bipy配合物作为多功能催化剂在Knoevenagel缩合中的吸附性能增强
IF 3.5 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-10-23 DOI: 10.1007/s11164-025-05783-2
Rajashri Varadarasu, Denzil Britto Christopher Leslee, Jayapratha Gunasekaran, Narmatha Venkatesan, Shanmuga Bharathi Kuppannan

A new mixed ligands Cobalt complex of Schiff base and 2,2′-bipyridine was anchored onto the mesoporous MCM-41 to synthesize a highly efficient and reusable heterogeneous catalyst. The prepared heterogeneous catalyst was characterized by FT-IR, UV-DRS, PXRD, SEM-EDX, ICP-OES, HR-TEM, TGA, N2 adsorption and desorption and 13C-CP-MAS-NMR. The Salen-Co-MCM-41-bipy complex has been found as a more promising catalyst for Knoevenagel condensation of aryl/alkyl malononitriles using different kind of aldehydes with malononitrile in EtOH/H2O solvent mixture under room temperature with the yield upto 99%. The catalyst was performed well against a wide range of substrates, viz, the aldehydes of aryl, fused aryl, hetero and aliphatic compounds with a variety of substituents at various positions. Moreover, the effectiveness of our catalyst against large-scale reaction up to 2.5 g of substrate was also explained. The catalyst is recovered by simple filtration and reused up to five times without any loss in activity. Hot filtration test was explored the heterogeneous nature of the recovered catalyst. Previous reports were compared and discussed to spotlight the efficiency of our catalyst.

Graphical abstract

将希夫碱与2,2′-联吡啶的钴配合物固定在介孔催化剂MCM-41上,合成了一种高效、可重复使用的多相催化剂。采用FT-IR、UV-DRS、PXRD、SEM-EDX、ICP-OES、HR-TEM、TGA、N2吸附和脱附、13C-CP-MAS-NMR等手段对制备的多相催化剂进行了表征。Salen-Co-MCM-41-bipy配合物是一种较有前景的催化剂,用于不同醛类与丙二腈在EtOH/H2O溶剂混合物中室温下进行芳基/烷基丙二腈的Knoevenagel缩合反应,收率可达99%。该催化剂在广泛的底物上表现良好,即芳基醛、熔融芳基、杂基和脂肪族化合物的醛在不同位置具有各种取代基。此外,我们的催化剂对2.5 g底物的大规模反应的有效性也得到了解释。催化剂通过简单的过滤回收,并重复使用多达五次而不损失任何活性。热过滤试验考察了回收催化剂的多相性。比较和讨论了前人的报道,以突出我们的催化剂的效率。图形抽象
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引用次数: 0
Novel CuFe2O4@SiO2.TiO2 nanocomposites for synthesis of 2,4,5-substituted imidazoles 合成2,4,5-取代咪唑的新型CuFe2O4@SiO2.TiO2纳米复合材料
IF 3.5 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-10-18 DOI: 10.1007/s11164-025-05729-8
Zahra Moghadasi, Vicky Jain, Suhas Ballal, Munthar Kadhim Abosaoda, Abhayveer Singh, T. Krithiga, Subhashree Ray

The synthesis of 2,4,5-substituted imidazoles has garnered significant attention due to the diverse biological activities exhibited by these compounds. In this study, we report a novel approach utilizing copper ferrite-coated silica–titania nanocomposites, CuFe2O4@SiO2.TiO2, as an efficient catalyst for the one-pot synthesis of 2,4,5-substituted imidazoles. The reaction protocol involves the condensation of aryl aldehydes, benzil, and an ammonia source (ammonium acetate) under mild conditions. The synthesized nanocomposite catalyst demonstrates impressively high catalytic activity and selectivity, achieving good yields of the desired imidazole derivatives. Comprehensive characterization of the nanocomposites using techniques such as FT-IR, XRD, SEM, and TEM confirmed the successful synthesis and morphology of the catalyst. The catalyst’s effectiveness highlighted its recyclability and stability over six reaction cycles, making it a promising candidate for green synthetic methodologies. The optimized reaction conditions achieved excellent yields within a short reaction time and showcased the potential of this nanocomposite in facilitating green chemistry practices. This work highlights that the versatility of CuFe2O4@SiO2.TiO2 nanocomposites in organic synthesis opens new avenues for developing efficient catalytic systems to prepare biologically significant heterocycles, instilling hope for a more sustainable future in the field of chemistry.

Graphical Abstract

2,4,5-取代咪唑的合成由于其具有多种生物活性而受到广泛关注。在这项研究中,我们报告了一种利用铁氧体铜涂层的二氧化硅-二氧化钛纳米复合材料CuFe2O4@SiO2.TiO2作为一锅合成2,4,5-取代咪唑的有效催化剂的新方法。反应方案包括芳醛、苯和氨源(醋酸铵)在温和条件下的缩合。所合成的纳米复合催化剂表现出令人印象深刻的高催化活性和选择性,获得了期望的咪唑衍生物的良好收率。利用FT-IR, XRD, SEM和TEM等技术对纳米复合材料进行了综合表征,证实了催化剂的成功合成和形貌。催化剂的有效性突出了其在六个反应周期内的可回收性和稳定性,使其成为绿色合成方法的有希望的候选者。优化后的反应条件在较短的反应时间内获得了优异的产率,显示了该纳米复合材料在促进绿色化学实践方面的潜力。这项工作强调了CuFe2O4@SiO2.TiO2纳米复合材料在有机合成中的多功能性,为开发高效的催化系统来制备具有生物意义的杂环开辟了新的途径,为化学领域更可持续的未来注入了希望。图形抽象
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引用次数: 0
Study of substrate–organocatalyst interactions in the model Knoevenagel mechanochemical condensation Knoevenagel机械化学缩合模型中底物-有机催化剂相互作用的研究
IF 3.5 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-10-17 DOI: 10.1007/s11164-025-05762-7
Syarifah Iliya Nor Za’im, Rita Sharmila Dewi, Mohd Rafie Johan, Nader Ghaffari Khaligh

In developing effective catalytic systems, understanding the interaction between reactant(s) and organocatalysts plays a crucial role in establishing the structure–activity relationship (SAR) in catalysis. This work investigated the interaction between imidazole, an organocatalyst, with the reactants in the Knoevenagel condensation of 2-chlorobenzaldehyde with malononitrile and ethyl cyanoacetate. Due to the solvent's impact on plausible interactions between reactants, organocatalysts, and intermediates, the study was conducted using FTIR and 1D NMR spectroscopic techniques. There was a correlation between the reduction of the acid methylene group intensity in 13C NMR spectra and the activity of acid methylene compounds. A reduction in α-carbon intensity of 75% and 23% for the malononitrile and ethyl cyanoacetate, respectively, was observed in the presence of one equivalent of imidazole. Moreover, the study introduced a greener and more sustainable solid-state procedure for the gram-scale preparation of 2-chlorobenzylidene malononitrile and 2-chlorobenzylidene cyanoacetic acid ethyl ester using a catalytic loading of imidazole, demonstrating the economic and practical aspects of the slurry mechanochemical process. The crystalline pure products could be isolated directly from an ethanol solution, and the residue containing imidazole was used in the next reactions without purification or activation after removing ethanol with a rotary evaporator.

Graphical abstract

在开发有效的催化体系中,了解反应物与有机催化剂之间的相互作用对于建立催化的构效关系(SAR)起着至关重要的作用。研究了有机催化剂咪唑在2-氯苯醛与丙二腈和氰乙酸乙酯的Knoevenagel缩合反应中与反应物的相互作用。由于溶剂对反应物、有机催化剂和中间体之间可能的相互作用的影响,研究使用FTIR和1D NMR光谱技术进行。13C核磁共振光谱中酸性亚甲基强度的降低与酸性亚甲基化合物的活性之间存在相关性。在咪唑的存在下,丙二腈和氰乙酸乙酯的α-碳强度分别降低了75%和23%。此外,该研究还介绍了一种更环保、更可持续的固体工艺,用于使用咪唑催化负载制备克级2-氯苄二烯丙二腈和2-氯苄二烯氰乙酸乙酯,展示了浆料机械化学工艺的经济和实用方面。结晶纯产物可直接从乙醇溶液中分离得到,含咪唑的残渣经旋转蒸发器脱除乙醇后,无需提纯或活化即可用于下一反应。图形抽象
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Research on Chemical Intermediates
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