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Nanoscale covalent organic frameworks for drug delivery: Linking structure and surface to stimuli-responsive release 用于药物递送的纳米级共价有机框架:连接结构和表面以刺激反应释放
IF 23.5 1区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-05-15 Epub Date: 2026-01-31 DOI: 10.1016/j.ccr.2026.217617
Ghasem Rezanejade Bardajee , Hossein Mahmoodian , Amirhosein Amini , Mahdieh Sharifi , Mohsen Adeli , Rajender Boddula
Covalent organic frameworks (COFs), particularly nanoscale COFs (NCOFs), have emerged as architecturally precise, metal-free nanocarriers with the potential to mitigate persistent limitations of conventional delivery platforms, including premature leakage, dilution-driven destabilization, and limited microenvironmental responsiveness, in appropriately designed systems. High loading, prolonged retention, and stimulus-triggered release have been reported, enabled by crystalline, permanent porosity combined with chemically programmable backbones and pore surfaces. In this review, a chemically grounded design framework is presented in which drug-delivery performance is linked to three interdependent variables: linkage chemistry, by which the balance between stability and triggerability is defined, namely, acid-labile, redox-responsive, ROS-responsive, or long-lived backbones; framework architecture and pore geometry, by which surface area, diffusion pathways, confinement, and partitioning are regulated; and surface and interface engineering, including postsynthetic modification (PSM), polymer coronas, and ligand decoration, by which colloidal stability, pharmacokinetics, protein corona formation, and cellular trafficking are governed. Although discussed as three variables for clarity, they are frequently coupled in practice; for instance, surface functionalization or polymer coronas can alter adequate pore accessibility and apparent crystallinity, and defects or terminations can dominate local binding environments and transport pathways.
Mechanistic design routes are summarized for representative linkages and architectures, including 2D and 3D frameworks, core and shell particles, nanosheets, nanofibers, and hollow constructs, and the resulting impacts on loading capacity, retention strength, and on-demand release under pH, redox, and ROS, light, or enzymatic cues are synthesized across reported studies. Practical considerations affecting the transferability of conclusions, including mass-balanced loading and release, trigger validation, stability budgets, and benchmarkable characterization packages, are highlighted alongside scalability and biointerface constraints. Actionable guidelines are provided for the rational selection of linkage, architecture, and surface and interfacial chemistry to engineer NCOF nanocarriers toward robust circulation and spatially and temporally programmed drug release.
共价有机框架(COFs),特别是纳米级COFs (NCOFs),已经成为一种结构精确、无金属的纳米载体,在适当设计的系统中,有可能减轻传统输送平台的持续局限性,包括过早泄漏、稀释驱动的不稳定和有限的微环境响应性。据报道,通过结晶、永久孔隙与化学可编程骨架和孔隙表面相结合,实现了高负载、长时间滞留和刺激触发释放。在这篇综述中,提出了一个基于化学的设计框架,其中药物传递性能与三个相互依存的变量相关联:连锁化学,通过它定义稳定性和可触发性之间的平衡,即酸不稳定、氧化还原反应、ros反应或长寿命骨架;框架结构和孔隙几何形状,通过它们可以调节表面积、扩散路径、约束和分区;表面和界面工程,包括合成后修饰(PSM)、聚合物冠和配体修饰,通过这些修饰,胶体稳定性、药代动力学、蛋白质冠形成和细胞运输受到控制。虽然为了清楚起见,我们将它们作为三个变量来讨论,但它们在实践中经常是耦合的;例如,表面功能化或聚合物电晕可以改变足够的孔隙可达性和明显的结晶度,缺陷或终止可以支配局部结合环境和运输途径。本文总结了具有代表性的连接和结构的机械设计路线,包括2D和3D框架、核和壳颗粒、纳米片、纳米纤维和空心结构,并综合了这些研究对负载能力、保持强度和pH、氧化还原和ROS、光或酶线索下的按需释放的影响。影响结论可转移性的实际考虑因素,包括质量平衡加载和释放、触发验证、稳定性预算和基准表征包,以及可扩展性和生物界面限制。为合理选择链接、结构、表面和界面化学来设计nof纳米载体,以实现稳健的循环和空间和时间程序化的药物释放,提供了可操作的指导方针。
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引用次数: 0
Chiral nanomaterials for oncology and beyond: advancing disease treatment 用于肿瘤及其他领域的手性纳米材料:推进疾病治疗
IF 23.5 1区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-05-15 Epub Date: 2026-02-03 DOI: 10.1016/j.ccr.2026.217644
Jie Feng , Ya-Nan Zhai , Zhi-Lin Dong, Yan Geng, Yu-Bin Dong
Chirality plays a fundamentally significant yet enigmatic role in governing essential chemical and biological processes. Over recent decades, researchers have widely studied the origin of chirality and its properties, extending chirality from molecules to inherently chiral nanoparticles and further to sophisticated chiral assemblies integrating organic materials, metals, semiconductors, and their hybrid systems. Notably, chiral nanomaterials exhibit superior biocompatibility that closely mimics native biological environments, offering distinct advantages for biomedical applications, and widely enhancing the efficacy of existing nanomaterials therapeutic regimens. With the rapid advancement of chiral nanomaterials in medicine and related fields, the selective interactions between chiral structures and biological systems and the mechanisms by which chirality regulates biological processes are being investigated at unprecedented depth, establishing a robust foundation for the functional exploitation of chiral nanomaterials. This review systematically examines the current classification methods, research progress, and therapeutic applications of chiral nanomaterials, with a special focus on their emerging advantages in cancer treatment. It also explores the transformative potential of chirality in existing nanotherapeutic strategies for cancer. Furthermore, the mechanisms underlying chirality-dependent therapeutic effects are discussed, along with potential challenges in clinical translation. Current evidence strongly indicates that chiral nanomaterials will play an increasingly critical role in the development of biomedical technologies. Collectively, these advancements pave the way for next-generation cancer treatment methods based on chiral nanotechnology.
手性在控制基本的化学和生物过程中起着重要而神秘的作用。近几十年来,研究人员对手性的起源及其性质进行了广泛的研究,将手性从分子扩展到固有的手性纳米粒子,并进一步扩展到集成有机材料、金属、半导体及其混合系统的复杂手性组件。值得注意的是,手性纳米材料表现出优异的生物相容性,可以模仿天然生物环境,为生物医学应用提供了独特的优势,并广泛增强了现有纳米材料治疗方案的功效。随着手性纳米材料在医学及相关领域的快速发展,手性结构与生物系统之间的选择性相互作用以及手性调控生物过程的机制正得到前所未有的深入研究,为手性纳米材料的功能开发奠定了坚实的基础。本文系统地综述了手性纳米材料的分类方法、研究进展和治疗应用,重点介绍了手性纳米材料在癌症治疗中的新优势。它还探讨了手性在现有的纳米癌症治疗策略中的变革潜力。此外,本文还讨论了手性依赖性治疗效果的潜在机制,以及临床转化中的潜在挑战。目前的证据有力地表明,手性纳米材料将在生物医学技术的发展中发挥越来越重要的作用。总的来说,这些进步为基于手性纳米技术的下一代癌症治疗方法铺平了道路。
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引用次数: 0
Recent advances in the removal of fluorocarbons: a review based on pollutant sources, sorts, removal technologies and mechanisms 碳氟化合物去除的最新进展:基于污染源、种类、去除技术和机制的综述
IF 23.5 1区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-05-15 Epub Date: 2026-02-03 DOI: 10.1016/j.ccr.2026.217647
Ziyan Chen , Jin Zhang , Na Gao , Lingpeng Lu , Bin Li
It is well known that industrialization leads to an increase in the emissions of fluorocarbons (FCs) in the atmosphere. These compounds pose a significant threat to ecosystems and human health due to their high global warming potential (GWP) and long lifetime. In recent years, many studies and developments have been conducted on the degradation and removal technologies of FCs, including methods such as adsorption, incineration, plasma, thermal catalytic, photocatalysis and catalytic hydrolysis. This review aims to comprehensively interpret and summarize the research progress for the removal of FCs in air pollution. The sources, sorts, hazards, applications and emission characteristics of FCs is detailed analyzed. It systematically summarizes research advances in removal methods and materials, offers a critical comparison of different decomposition technologies, and highlights respective advantages and limitations, and typical adsorbents and catalysts are also summarized. Furthermore, the removal and decomposition mechanisms for different technologies of major FCs are comprehensively outlined, with a detailed examination of the involved active sites, intermediate products, and final outputs, and the mechanisms of deactivation and reactivation for catalyst and adsorbent were also discussed. The reaction pathways at different active sites were analyzed in detail through the typical CF4 under the catalytic hydrolysis that are widely concerned, and key factors affecting removal efficiency are explored. Finally, current challenges and future research directions in FCs decomposition and removal are summarized. We believe that this review will provide valuable insights and theoretical references for the selection and development of future technologies for the efficient removal of FCs from the atmosphere.
众所周知,工业化导致大气中碳氟化合物(fc)排放量的增加。这些化合物由于其高全球变暖潜势(GWP)和长寿命,对生态系统和人类健康构成重大威胁。近年来,对氟碳化合物的降解和去除技术进行了许多研究和发展,包括吸附、焚烧、等离子体、热催化、光催化和催化水解等方法。本文旨在对大气污染中氟化碳的去除研究进展进行全面解读和总结。详细分析了氟化碳的来源、种类、危害、应用和排放特性。系统总结了去除方法和材料的研究进展,对不同的分解技术进行了批判性的比较,突出了各自的优势和局限性,并总结了典型的吸附剂和催化剂。此外,全面概述了不同技术对主要氟化碳的去除和分解机理,详细分析了所涉及的活性位点、中间产物和最终产出,并讨论了催化剂和吸附剂的失活和再活化机理。通过对目前广泛关注的典型CF4催化水解反应,详细分析了不同活性位点的反应途径,探讨了影响去除率的关键因素。最后,总结了目前存在的挑战和未来的研究方向。我们相信这一综述将为未来选择和发展有效去除大气中氟化碳的技术提供有价值的见解和理论参考。
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引用次数: 0
Engineering porphyrin-derived nanomaterials for multimodal antibacterial therapy: From rational design to practical applications 用于多模态抗菌治疗的工程卟啉衍生纳米材料:从合理设计到实际应用
IF 23.5 1区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-05-15 Epub Date: 2026-02-04 DOI: 10.1016/j.ccr.2026.217635
Xiao-Ru Sun , Jun Li , Ren-Ju Chen , Rui Wang , Ze-Wen Yu , Hui-Yan Sun , He Huang , Yu Xiao , Yan-Mei Zhang
The emergence of multidrug-resistant bacteria (MDR) due to antibiotic misuse presents a critical global health challenge. To address the challenge, engineered tailored porphyrin-derived nanomaterials have been explored as promising platforms for multimodal antibacterial therapies. Despite their significant potential, a systematic analysis of porphyrin-derived nanomaterials as multifunctional antimicrobial agents, encompassing their roles as sonosensitizers, nanozymes and drug carriers, is lacking. To fill this gap, this review focuses on the following core issues. Firstly, it provides a detailed analysis of the clinical potential of porphyrin-derived nanomaterials and the necessity and profound significance of composing this structured review with a theoretical framework of “structure-property-application”. The second part introduces the physicochemical properties of different types of porphyrin-derived nanomaterials. Building upon this foundation, the third part employs a “structure-activity relationship (SAR)” lens to progressively analyze strategies for enhancing antibacterial efficacy at molecular-, nanoscale- and multimode system-levels. After that, representative case studies in wastewater treatment, biomedicine and food industry are comprehensively summarized. Finally, critical discussions of current challenges regarding material stability, biosafety, and scalable production are discussed, along with forward-looking perspectives for future research directions
抗生素滥用导致的耐多药细菌(MDR)的出现是一项重大的全球卫生挑战。为了应对这一挑战,工程定制卟啉衍生纳米材料已被探索作为多模式抗菌治疗的有前途的平台。尽管卟啉衍生的纳米材料具有巨大的潜力,但缺乏对其作为多功能抗菌剂的系统分析,包括其作为声敏剂,纳米酶和药物载体的作用。为了填补这一空白,本文将重点讨论以下核心问题。首先,详细分析了卟啉类纳米材料的临床潜力,以及以“结构-性能-应用”的理论框架撰写这篇结构化综述的必要性和意义。第二部分介绍了不同类型卟啉衍生纳米材料的物理化学性质。在此基础上,第三部分采用“构效关系(SAR)”视角,逐步分析在分子、纳米尺度和多模系统水平上增强抗菌功效的策略。然后对污水处理、生物医药和食品行业的代表性案例进行了全面总结。最后,讨论了当前材料稳定性、生物安全性和可扩展生产方面的挑战,以及对未来研究方向的前瞻性观点
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引用次数: 0
Next-generation fuel cell technologies empowered by covalent organic frameworks-based materials: A review on emerging potential of COFs for functional membranes and catalytic advancements 以共价有机骨架材料为基础的下一代燃料电池技术:COFs在功能膜和催化方面的新潜力综述
IF 23.5 1区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-05-15 Epub Date: 2026-02-03 DOI: 10.1016/j.ccr.2026.217669
Ahmad Husain , Prem Gunnasegaran , Mohtaram Danish , Dong-Eun Lee , Wan-Kuen Jo
Covalent Organic Frameworks (COFs) have emerged as a highly versatile class of crystalline porous polymers with tunable structures and chemical functionalities, offering immense promise for energy-related applications. Among these, fuel cells represent a critical domain where COF-based materials have begun to demonstrate significant potential, both as proton-conducting membranes and as electrocatalysts for key reactions such as the oxygen reduction reaction (ORR). This review comprehensively highlights recent progress in the use of COF-based materials for fuel cell applications, with a particular focus on their dual functionality. In the membrane domain, these materials have shown excellent proton conductivities under both humidified and anhydrous conditions, along with good thermal and mechanical stability, making them viable alternatives to conventional membranes in proton exchange membrane fuel cells (PEMFCs). Their ordered channels, tunable surface chemistry, and chemical stability offer advantages for tailoring ion transport. However, their application in anion exchange membrane fuel cells (AEMFCs) remains underdeveloped and calls for greater material innovation. As electrocatalysts, both metal-free and metal-coordinated, they have exhibited outstanding ORR activity, often comparable to or surpassing platinum-based benchmarks, and have been successfully integrated into membrane electrode assemblies (MEAs) in PEMFCs, AEMFCs, and microbial fuel cells (MFCs). The review also discusses standalone ORR studies to demonstrate the intrinsic catalytic potential of COF-based materials. Finally, it outlines critical future directions, including the use of computational screening, machine learning, and hybrid composite strategies to unlock the full capabilities of COFs in real-world fuel cell systems. This work positions COFs as a promising next-generation platform for sustainable and efficient fuel cell technologies.
共价有机框架(COFs)是一种具有可调结构和化学功能的高用途晶体多孔聚合物,在能源相关应用中具有巨大的前景。其中,燃料电池代表了一个关键领域,cof基材料已经开始显示出巨大的潜力,无论是作为质子导电膜还是作为关键反应的电催化剂,如氧还原反应(ORR)。本文全面介绍了燃料电池中基于cof的材料的最新进展,并特别关注了它们的双重功能。在膜领域,这些材料在加湿和无水条件下都表现出优异的质子导电性,以及良好的热稳定性和机械稳定性,使其成为质子交换膜燃料电池(pemfc)中传统膜的可行替代品。它们的有序通道、可调的表面化学和化学稳定性为定制离子传输提供了优势。然而,它们在阴离子交换膜燃料电池(aemfc)中的应用仍然不发达,需要更大的材料创新。作为无金属和金属配位的电催化剂,它们具有出色的ORR活性,通常可与铂基基准相媲美或超过,并已成功集成到pemfc, aemfc和微生物燃料电池(mfc)的膜电极组件(MEAs)中。本文还讨论了独立的ORR研究,以证明cof基材料的内在催化潜力。最后,它概述了未来的关键方向,包括使用计算筛选、机器学习和混合复合策略来解锁COFs在现实世界燃料电池系统中的全部功能。这项工作将COFs定位为可持续和高效的下一代燃料电池技术平台。
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引用次数: 0
Advanced aqueous eutectic electrolyte: Bridging the development of high-performance aqueous zinc-ion batteries 先进的水共晶电解质:桥接高性能水锌离子电池的发展
IF 23.5 1区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-05-15 Epub Date: 2026-02-03 DOI: 10.1016/j.ccr.2026.217665
Jing-Yu Wang , Zheng-Han Yang , Jing Li , Peng-Fei Wang , Zong-Lin Liu , Jie Shu , Ting-Feng Yi
Aqueous electrolytes as a crucial component of aqueous zinc-ion batteries (AZIBs), directly influence the stability and cycle life of AZIBs through their composition and performance. However, conventional aqueous electrolytes subject AZIBs to issues such as dendrite growth and cathode dissolution, compromising battery performance. To address this, researchers combined the advantages of deep eutectic solvents (DESs) systems and aqueous electrolyte systems to develop aqueous eutectic electrolytes (AEEs) with unique structures. Under the influence of complex intermolecular interactions between AEEs components, these electrolytes remain liquid at lower temperatures while significantly suppressing the activity and quantity of H2O within the electrolyte. This approach effectively enhances both battery safety and cycling performance. To comprehensively understand AEEs for AZIBs, this review systematically outlines their characteristics, fundamental compositions, and testing methods for evaluating electrochemical performance. Subsequently, AEEs are categorized into water-cosolvent eutectic electrolytes and hydrated eutectic electrolytes (HEEs), with definitions and recent advancements for each category presented. Furthermore, an innovative analysis is presented on the role of constituent components in AEEs and their corresponding strategies for improving electrolyte stability, cathode, and anode performance. In conclusion, the persistent challenges and promising future research directions are summarized, providing an important reference for the development of novel eutectic electrolytes.
水溶液电解质作为水基锌离子电池的重要组成部分,其组成和性能直接影响着水基锌离子电池的稳定性和循环寿命。然而,传统的水性电解质会使azib受到枝晶生长和阴极溶解等问题的影响,从而影响电池的性能。为了解决这个问题,研究人员结合了深共晶溶剂(DESs)体系和水电解质体系的优势,开发了具有独特结构的水共晶电解质(AEEs)。在AEEs组分之间复杂的分子间相互作用的影响下,这些电解质在较低温度下保持液态,同时显著抑制了电解质中H2O的活性和数量。这种方法有效地提高了电池的安全性和循环性能。为了全面了解azib的AEEs,本文系统地概述了它们的特性、基本组成和电化学性能评估的测试方法。随后,将aee分为水-共溶剂共晶电解质和水合共晶电解质(HEEs),并介绍了每一类的定义和最新进展。此外,本文还创新性地分析了AEEs中组成成分的作用,以及它们相应的改善电解质稳定性、阴极和阳极性能的策略。最后总结了当前共晶电解质存在的挑战和未来的研究方向,为新型共晶电解质的开发提供了重要参考。
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引用次数: 0
Integration of graphitic carbon nitrides with coordination complexes for photocatalytic applications 石墨碳氮与配位配合物在光催化应用中的集成
IF 23.5 1区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-05-15 Epub Date: 2026-01-28 DOI: 10.1016/j.ccr.2026.217612
Charul Sharma , Binitendra Naath Mongal
Graphitic carbon nitride (g-C3N4), a metal free polymeric semiconductor is attracting great attention due to lower band-gap (∼2.7 eV), charge separation efficiency, chemically inert and non-toxic nature in presence of abundant earth elements. However, pure g-C3N4 suffers from limited visible-light absorption and charge recombination limiting its photocatalytic efficiency. To overcome these issues, recent research has been focused on formation of heterojunctions with g-C3N4. This review article focuses on integration of g-C3N4 with metal complexes to improve its photocatalytic efficiency. The innovative methods for preparing the hybrid photocatalysts with g-C3N4 and molecular metal complexes via covalent and non-covalent interactions with its effect on surface chemistry and electronic structure have been thoroughly discussed. Furthermore, the article focuses on structural design of the prepared composites, interfacial charge transfer between g-C3N4 and metal complexes, along with their applications in photocatalytic CO2 reduction, H2 evolution, organic conversions and dye degradation. The comprehensive review will help in identifying pathways for effective utilization of g-C3N4/metal complex composites in driving various photocatalytic reactions.
石墨化氮化碳(g-C3N4)是一种无金属聚合物半导体,由于其低带隙(~ 2.7 eV)、电荷分离效率、化学惰性和在丰富的土元素存在下无毒等特性而备受关注。然而,纯g-C3N4的可见光吸收和电荷重组有限,限制了其光催化效率。为了克服这些问题,最近的研究集中在与g-C3N4形成异质结上。本文综述了g-C3N4与金属配合物的整合以提高其光催化效率的研究进展。讨论了通过共价和非共价相互作用制备g-C3N4与分子金属配合物杂化光催化剂的新方法及其对表面化学和电子结构的影响。此外,本文重点介绍了制备的复合材料的结构设计、g-C3N4与金属配合物之间的界面电荷转移,以及它们在光催化CO2还原、H2析出、有机转化和染料降解等方面的应用。本文综述将有助于确定g-C3N4/金属配合物复合材料在各种光催化反应中的有效利用途径。
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引用次数: 0
Pushing the boundaries: The path of mechanosynthesis toward the assembly of supramolecular organic frameworks 突破边界:机械合成通往超分子有机框架组装的道路
IF 23.5 1区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-05-15 Epub Date: 2026-01-27 DOI: 10.1016/j.ccr.2026.217600
Danilo Marchetti, Riccardo Testa, Alessandro Pedrini, Chiara Massera
Supramolecular organic frameworks (SOFs), synthetic frameworks assembled via non-covalent interactions, are being extensively studied for their applications as porous functional solids endowed with flexibility, reversibility and tunability of stimuli-responsive properties. This review explores the use of mechanosynthesis as a versatile strategy for their rational design and green synthesis, while expanding their structural and functional diversity. After an overview of the path followed by supramolecular mechanochemistry from the assembly of cocrystals to the complexation of host-guest systems in the solid state, we have detailed the mechanosynthesis of hydrogen-bonded organic frameworks (HOFs) and the less-explored halogen-bonded organic frameworks (XOFs), highlighting the advantages of solid-state methods in promoting reactivity, sustainability, and access to otherwise unattainable architectures.
超分子有机骨架(SOFs)是通过非共价相互作用组装而成的合成骨架,作为具有柔性、可逆性和可调性的多孔功能固体,正受到广泛的研究。这篇综述探讨了机械合成作为其合理设计和绿色合成的通用策略,同时扩大了其结构和功能的多样性。在概述了超分子机械化学从共晶组装到固态主客系统络合的路径之后,我们详细介绍了氢键有机框架(HOFs)和较少探索的卤素键有机框架(XOFs)的机械合成,强调了固态方法在促进反应性、可持续性和获得其他无法实现的结构方面的优势。
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引用次数: 0
From coordination spheres to catalytic sites: Defect engineering in metal oxide photocatalysts 从配位球到催化位点:金属氧化物光催化剂的缺陷工程
IF 23.5 1区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-05-15 Epub Date: 2026-01-27 DOI: 10.1016/j.ccr.2026.217614
Yan Lu , Seunghyun Weon , Ki-Hyun Kim
Lattice defects in metal oxide semiconductors, once regarded as performance-limiting flaws, are recognized as powerful tools for enhancing photocatalytic activity. These structural imperfections, including oxygen vacancies (Vo), cation deficiencies, interstitials, and dopant-induced distortions, are not mere flaws but products of deliberate defect engineering rooted in coordination chemistry principles. The deliberate distortion of the local coordination environment around metal centers introduces specific defects that, in turn, directly modulate the electronic band structure, redefine surface properties, and alter charge carrier transport. In the photocatalytic oxidation of volatile organic compounds (VOCs), defect engineering enables improved light absorption, more efficient charge separation, and increased generation of reactive oxygen species. This review deciphers how engineered defects in metal oxides boost photocatalytic removal performance of VOCs. The connection between synthesis, characterization, and mechanism is thus established to offer mechanistic insights into how coordination sphere distortion at metal sites governs the photomineralization of VOCs. Selected case studies, including TiO₂, ZnO, WO₃, and CeO₂, are used to highlight key structure–function relationships and real-world performance. The review concludes by addressing critical challenges in quantifying and stabilizing defects, scaling up defect-engineered materials, and designing catalysts with enhanced selectivity, sustainability, and long-term usability.
金属氧化物半导体中的晶格缺陷曾经被认为是限制性能的缺陷,现在被认为是增强光催化活性的有力工具。这些结构缺陷,包括氧空位(Vo)、阳离子缺乏、间隙和掺杂剂引起的扭曲,不仅仅是缺陷,而是基于配位化学原理的故意缺陷工程的产物。金属中心周围局部配位环境的故意扭曲引入了特定的缺陷,这些缺陷反过来直接调节电子能带结构,重新定义表面性质,并改变电荷载流子输运。在挥发性有机化合物(VOCs)的光催化氧化中,缺陷工程可以改善光吸收,更有效地分离电荷,并增加活性氧的产生。这篇综述揭示了金属氧化物中的工程缺陷如何提高VOCs光催化去除性能。因此,建立了合成、表征和机制之间的联系,为金属位点的配位球畸变如何控制VOCs的光矿化提供了机制上的见解。选定的案例研究,包括TiO₂、ZnO、WO₃和CeO₂,用来突出关键的结构功能关系和现实世界的性能。本文总结了在量化和稳定缺陷、扩大缺陷工程材料和设计具有增强选择性、可持续性和长期可用性的催化剂方面的关键挑战。
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引用次数: 0
Theoretical investigations on the activation of Silanes by rare-earth complexes: Mechanisms, bonding, and catalytic implications 稀土配合物对硅烷活化的理论研究:机理、键和催化意义
IF 23.5 1区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-05-15 Epub Date: 2026-02-03 DOI: 10.1016/j.ccr.2026.217668
Jiafeng Zhang , Xiaoxia Wu , Meirong Song , Laurent Maron
The activation of E–H bonds (E = Si, B, C, etc.) by rare-earth complexes has emerged as a central topic in organometallic chemistry, due to its mechanistic diversity and its relevance to catalytic transformations. Among these, the cleavage and functionalization of silanes (SiH) by lanthanide and related complexes have drawn increasing attention, both experimentally and theoretically. Recent computational studies have unveiled a wealth of mechanistic insights, revealing that σ-bond metathesis constitutes the dominant pathway for SiH activation across most rare-earth elements, contrasting with oxidative addition mechanisms typical of transition metals. This review summarizes theoretical developments devoted to the activation of silanes by rare-earth complexes, emphasizing density functional theory (DFT) analyses, bonding descriptions, and trends across the lanthanide series. Theoretical models, including Cp₂LnH and bis(amidinate) systems, are discussed in connection with experimental data, providing a coherent picture of structure–reactivity relationships. Finally, perspectives on ligand effects, periodic trends, and catalytic applications are outlined to guide future design of rare-earth-based hydrosilylation catalysts.
稀土配合物对E - h键(E = Si, B, C等)的激活由于其机制的多样性和与催化转化的相关性,已经成为有机金属化学中的一个中心话题。其中,镧系元素及其配合物对硅烷(SiH)的解理和功能化在实验和理论上都引起了越来越多的关注。最近的计算研究揭示了丰富的机制见解,揭示了σ键复分解是大多数稀土元素SiH活化的主要途径,与典型的过渡金属氧化加成机制形成对比。本文综述了稀土配合物激活硅烷的理论进展,重点介绍了密度泛函理论(DFT)分析、键描述和镧系化合物的发展趋势。理论模型,包括Cp₂LnH和双(氨基)系统,讨论了与实验数据的联系,提供了结构-反应性关系的连贯画面。最后,概述了配体效应、周期趋势和催化应用方面的观点,以指导稀土基硅氢化催化剂的未来设计。
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Coordination Chemistry Reviews
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