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Decoding the Catalytic Potential of Dinuclear 1st-Row Transition Metal Complexes for Proton Reduction and Water Oxidation 解码双核第一行过渡金属配合物对质子还原和水氧化的催化潜力。
IF 7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-12-10 DOI: 10.1002/tcr.202400170
Dr. Manaswini Raj, Prof. Sumanta Kumar Padhi

The growing interest in renewable energy sources has led to a significant focus on artificial photosynthesis as a means of converting solar energy into lucrative and energy-dense carbonaceous fuels. First-row transition metals have thus been brought to light in the search for efficient and high-performance homogenous molecule catalysts that can accelerate energy transformation and reduce overpotentials during the catalytic process. Their dinuclear complexes have opportunities to enhance the efficiency and stability of these molecular catalysts, primarily for the hydrogen evolution reaction (HER) and water oxidation reaction (WOR). Recently, our group improved the catalytic activity, efficiencies, and stability of dinuclear molecular catalysts, particularly toward HER. Although one dinuclear complex has been tested for WOR, it demonstrated activity as water oxidation precatalysts. First-row transition metals are a great option for sustainable catalysis because they are readily available, reasonably priced, and have multifaceted coordination chemistry. Examples of these metals are cobalt, copper, and manganese. The structure-catalytic performance relationships of this first-row transition metal-based dinuclear catalysts are noteworthily interpreted in this account, providing avenues for optimizing their performance and advancing the development of sustainable and effective energy conversion technologies.

对可再生能源日益增长的兴趣导致了人工光合作用作为一种将太阳能转化为利润丰厚且能量密集的碳质燃料的手段的重大关注。因此,在寻找高效、高性能的均质分子催化剂的过程中,第一排过渡金属已经被发现,这些催化剂可以加速能量转化,减少催化过程中的过电位。它们的双核配合物有机会提高这些分子催化剂的效率和稳定性,主要用于析氢反应(HER)和水氧化反应(WOR)。最近,我们的研究小组提高了双核分子催化剂的催化活性、效率和稳定性,特别是对HER的催化。虽然对一个双核配合物进行了WOR测试,但它显示出作为水氧化预催化剂的活性。第一排过渡金属是可持续催化的一个很好的选择,因为它们容易获得,价格合理,并且具有多方面的配位化学。这些金属的例子有钴、铜和锰。这一第一排过渡金属基双核催化剂的结构-催化性能关系在本报告中得到了值得注意的解释,为优化其性能和促进可持续和有效的能量转换技术的发展提供了途径。
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引用次数: 0
Molecular Heterogeneous Photocatalysts for Visible-Light-Driven CO2 Reduction. 可见光驱动CO2还原的分子非均相光催化剂。
IF 7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-12-10 DOI: 10.1002/tcr.202400202
Yuanyuan Qi, Hai Sun, Ping She, Jun-Sheng Qin, Heng Rao

Photoreduction of CO2 to high-value chemical fuels presents an effective strategy to reduce reliance on fossil fuels and mitigate climate change. The development of a photocatalyst characterized by superior activity, high selectivity, and good stability is a critical issue for PCR. Molecular heterogeneous photocatalytic systems integrate the advantages of both homogeneous and heterogeneous catalysts, creating a synergistic enhancement effect that increases photocatalytic performance. This review summarizes recent advancements in molecular heterogeneous photocatalysts for CO2 reduction. Much of the discussion focuses on the types of molecular heterogeneous photocatalysts, and their photocatalytic performance in CO2 reduction is summarized. The synthesis strategies for molecular heterogeneous photocatalysts are thoroughly discussed. Finally, the challenges and future prospects of molecular heterogeneous photocatalysts for PCR are addressed.

二氧化碳光还原为高价值化学燃料是减少对化石燃料依赖和减缓气候变化的有效策略。开发具有高活性、高选择性和良好稳定性的光催化剂是聚合酶链反应的关键问题。分子非均相光催化系统结合了均相和非均相催化剂的优点,产生了协同增强效应,提高了光催化性能。本文综述了二氧化碳还原分子非均相光催化剂的研究进展。本文主要讨论了分子非均相光催化剂的类型,并对其在CO2还原中的光催化性能进行了综述。深入讨论了分子非均相光催化剂的合成策略。最后,对分子非均相光催化剂在PCR中的应用前景进行了展望。
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引用次数: 0
Harnessing Ruthenium and Copper Catalysts for Formate Dehydrogenase Reactions 利用钌和铜催化剂催化甲酸脱氢酶反应。
IF 7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-12-04 DOI: 10.1002/tcr.202400172
Aman Mishra, Sumanta Kumar Padhi

Formic acid (HCOOH) is a promising source of hydrogen energy that can be used to produce hydrogen in a more economical and ecological way. Formic acid is a simple carboxylic acid with a high hydrogen concentration and is generally stable, making it useful as a hydrogen transporter. Catalytic dehydrogenation is usually used to extract hydrogen from formic acid; this process releases hydrogen gas and yields carbon dioxide as a byproduct. Comparing this technology to conventional hydrogen generation methods, there are several benefits, such as the utilization of the formic acid handling infrastructure already in place and the possibility of a simpler integration into different energy systems. Notwithstanding, several obstacles persist, including enhancing the effectiveness of the dehydrogenation procedure and reducing the ecological consequences of the correlated carbon dioxide discharges. Catalysts, reaction conditions, and carbon collection and utilization methodologies are all being researched further. The development of Ru and Cu-based catalysts for the catalytic breakdown of HCOOH into CO2 and H2 is the main topic of this account. Herein, the focus is on the kinetic studies of HCOOH dehydrogenation, encompassing mechanistic investigations that consider intermediate studies and DFT calculations.

甲酸(HCOOH)是一种很有前途的氢能源,可以更经济、更生态地用于制氢。甲酸是一种简单的羧酸,具有高浓度的氢,通常是稳定的,使其成为一种有用的氢转运体。甲酸中氢的提取通常采用催化脱氢法;这个过程释放氢气并产生二氧化碳作为副产品。与传统的制氢方法相比,该技术有几个优点,比如利用现有的甲酸处理基础设施,以及更简单地集成到不同的能源系统中。尽管如此,仍然存在一些障碍,包括提高脱氢过程的有效性和减少相关二氧化碳排放的生态后果。催化剂、反应条件、碳收集利用方法等都在进一步研究中。Ru基和cu基催化剂的开发用于催化HCOOH分解成CO2和H2是本报告的主要主题。本文的重点是HCOOH脱氢的动力学研究,包括考虑中间研究和DFT计算的机理研究。
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引用次数: 0
Advancements and Challenges in Adsorption-Based Carbon Capture Technology: From Fundamentals to Deployment 基于吸附的碳捕获技术的进展和挑战:从基础到部署。
IF 7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-12-04 DOI: 10.1002/tcr.202400188
Hamid Zentou, Mansur Aliyu, Mahmoud A. Abdalla, Omar Y. Abdelaziz, Bosirul Hoque, Ahmed M. Alloush, Islam M. Tayeb, Kumar Patchigolla, Mahmoud M. Abdelnaby

Carbon dioxide (CO2) adsorption on solid sorbents represents a promising technology for separating carbon from different sources and mitigating anthropogenic emissions. The complete integration of carbon capture technologies in various industrial sectors will be crucial for a sustainable, low-carbon future. Despite developing new sorbents, a comprehensive strategy is essential to realize the full potential and widespread adoption of CO2 capture technologies, including different engineering aspects. This study discusses the pathway for deploying adsorption-based carbon capture technology in fundamental material science aspects, thermo-physical properties behavior at the molecular level, and industrial pilot scale demonstrations. When integrated with process simulation and economic evaluations, these techniques are instrumental in enhancing the efficiency and cost-effectiveness of the capturing processes. While advancements in adsorption-based carbon capture technologies have been notable, their deployment still encounters significant hurdles, including technical, economic, and environmental challenges. Leveraging hybrid systems, renewable energy integration, and the strategic application of emerging machine learning techniques appear promising to address global warming effectively and will consequently be discussed in this investigation.

固体吸附剂对二氧化碳的吸附是一种很有前途的分离不同来源碳和减少人为排放的技术。碳捕获技术在各个工业部门的全面整合对于可持续的低碳未来至关重要。尽管开发了新的吸附剂,但要实现二氧化碳捕获技术的全部潜力和广泛采用,包括不同的工程方面,一个全面的战略是必不可少的。本研究讨论了在基础材料科学方面、分子水平上的热物理性质行为和工业中试规模演示中应用基于吸附的碳捕获技术的途径。当与过程模拟和经济评估相结合时,这些技术有助于提高捕获过程的效率和成本效益。尽管基于吸附的碳捕获技术取得了显著的进步,但它们的部署仍然面临着重大障碍,包括技术、经济和环境方面的挑战。利用混合系统、可再生能源集成和新兴机器学习技术的战略应用似乎有望有效地解决全球变暖问题,因此将在本调查中进行讨论。
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引用次数: 0
Co3O4 Hybrid Electrocatalysts; Materials Description and Mechanistic Aspects Toward Hydrogen Production, Oxygen Evolution-Reduction, and CO2 Reduction Reactions. Co3O4混杂电催化剂;产氢,析氧-还原和二氧化碳还原反应的材料描述和机理方面。
IF 7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-12-04 DOI: 10.1002/tcr.202400166
Aneela Tahira, Mohsen Padervand, Elmuez Dawi, Umair Aftab, Shahnaz Ghasemi, Brigitte Vigolo, Matteo Tonezzer, Samina Bidmeshkipour, Masoud Baghernejad, Abdelkader Labidi, Eric Lichtfouse, Chuanyi Wang, Alberto Vomiero, Zafar Hussain Ibupoto

Controlling the adverse effects of global warming on human communities requires reducing carbon dioxide emissions and developing clean energy resources. Fossil fuel overuse damages the environment and raises sustainability concerns. As a resource-rich element, cobalt oxide hybrids have attracted considerable attention as low-priced and eco-friendly electrocatalysts. Alkaline solutions disperse Co3O4 easily despite its highly stable nature, which arises from the reverse spinel structures of Co. Metal oxides, nickel foam, polymeric frameworks, and carbon nanotubes have been successfully served to combine with the Co3O4 constructions for improving the electrocatalytic performance. To date, no comprehensive study has systematically investigated the relation between the cobalt oxide hybrid's physicochemical-electronic aspects and its catalytic features. This review mainly focuses on material design, fabrication, morphology, structural characteristics, and electroactivity, considering the critical factors towards practical applications. The economic impacts of the constructions and their expected contribution to large-scale utilizations are also demonstrated. Moreover, this research discusses the synergistic effects of crucial electrochemical parameters on sustainable energy production over the Co3O4-based hybrids. Finally, some beneficial conclusive suggestions are made based on emerging factors for real-world application. Future research in the field aiming at developing sustainable and clean energy production technologies can effectively benefit from the findings of this report.

控制全球变暖对人类社会的不利影响需要减少二氧化碳排放和开发清洁能源。化石燃料的过度使用会破坏环境,并引发对可持续性的担忧。钴氧化物作为一种资源丰富的元素,作为一种价格低廉、环境友好的电催化剂而备受关注。Co3O4由于Co的反尖晶石结构而具有高度稳定性,但碱性溶液容易分散Co3O4。金属氧化物、泡沫镍、聚合物框架和碳纳米管已成功地与Co3O4结构结合,以提高其电催化性能。迄今为止,还没有全面的研究系统地研究了氧化钴杂化物的物理化学电子方面与其催化特性之间的关系。本文主要综述了材料的设计、制造、形态、结构特性和电活性,并考虑了实际应用的关键因素。还论证了这些建设的经济影响及其对大规模利用的预期贡献。此外,本研究还讨论了关键电化学参数对co3o4基混合动力车可持续能源生产的协同效应。最后,根据新出现的因素,对实际应用提出了有益的结论性建议。未来该领域旨在发展可持续和清洁能源生产技术的研究可以有效地受益于本报告的发现。
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引用次数: 0
Combination Using Magnetic Iron Oxide Nanoparticles and Magnetic Field for Cancer Therapy 利用磁性纳米氧化铁粒子和磁场联合治疗癌症
IF 7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-28 DOI: 10.1002/tcr.202400179
Wenjun Sun, Xiaoxia Chai, Yuan Zhang, Tongyao Yu, Yuhua Wang, Wenzhe Zhao, Yanhua Liu, Dachuan Yin, Chenyan Zhang

Iron oxide nanoparticles (MNPs) demonstrate notable benefits in magnetic induction, attributed to their distinctive physical and chemical attributes. Emerging cancer treatment utilizing magnetic fields have also gathered increasing attention in the biomedical field. However, the defects of difficult dispersion and poor biocompatibility of MNPs seriously hinder their application. In order to overcome its inherent defects and maximize the therapeutic potential of MNPs, various functionalized MNPs have been developed, and numerous combined treatment methods based on MNPs have been widely studied. In this review, we compare and analyze the common nanoparticles based on MNPs with different sizes, shapes, and functional modifications. Additionally, we introduced the therapeutic mechanisms of the strategies, such as magnetically controlled targeting, magnetic hyperthermia, and magneto-mechanical effect, which based on the unique magnetic induction capabilities of MNPs. Finally, main challenges of MNPs as smart nanomaterials were also discussed. This review seeks to offer a thorough overview of MNPs in biomedicine and a new sight for their application in tumor treatment.

氧化铁纳米粒子(MNPs)因其独特的物理和化学属性,在磁感应方面表现出显著的优势。利用磁场治疗癌症的新方法也日益受到生物医学领域的关注。然而,MNPs 难以分散和生物相容性差的缺陷严重阻碍了其应用。为了克服其固有缺陷,最大限度地发挥 MNPs 的治疗潜力,人们开发了各种功能化 MNPs,并广泛研究了许多基于 MNPs 的综合治疗方法。在这篇综述中,我们比较和分析了基于不同尺寸、形状和功能修饰的 MNPs 的常见纳米粒子。此外,我们还介绍了基于 MNPs 独特磁感应能力的磁控靶向、磁热和磁力学效应等策略的治疗机制。最后,还讨论了 MNPs 作为智能纳米材料所面临的主要挑战。本综述旨在全面概述 MNPs 在生物医学中的应用,并为其在肿瘤治疗中的应用提供新的视角。
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引用次数: 0
Skeletal Editing via Transition-Metal-Catalyzed Nitrene Insertion 通过过渡金属催化的腈插入进行骨架编辑。
IF 7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-28 DOI: 10.1002/tcr.202400184
Pratibha Bhatti, Anjali Gupta, Shubham B. Chaudhari, Rahul K. Valmiki, Joydev K. Laha, Srimanta Manna

Metal-nitrenes are valuable reactive intermediates for synthesis and are widely used to construct biologically relevant scaffolds, complexes and functionalized molecules. The ring expansion of cyclic molecules via single-nitrogen-atom insertion via nitrene or metal-nitrenoid intermediates has emerged as a promising modern strategy for driving advantageous nitrogen-rich compound synthesis. In recent years, the catalytic insertion of a single nitrogen atom into carbocycles, leading to N-heterocycles, has become an important focus of modern synthetic approaches with applications in medicinal chemistry, materials science, and industry. Catalytic single-nitrogen-atom insertions have been increasing in prominence in modern organic synthesis due to their capability to construct high-value added nitrogen-containing heterocycles from simple feedstocks. In this review, we will discuss the rapidly growing field of skeletal editing via single-nitrogen-atom insertion using transition metal catalysis to access nitrogen-containing heterocycles, with a focus on nitrogen insertion across a wide spectrum of carbocycles.

金属烯属化合物是重要的活性合成中间体,被广泛用于构建生物相关的支架、配合物和功能化分子。通过腈或金属腈中间体插入单氮原子使环状分子扩环,已成为推动优势富氮化合物合成的一种前景广阔的现代策略。近年来,催化单个氮原子插入碳环并生成 N-杂环已成为现代合成方法的一个重要焦点,在药物化学、材料科学和工业中都有应用。催化单氮原子插入法在现代有机合成中的地位日益突出,因为它能从简单的原料中构建出高附加值的含氮杂环。在本综述中,我们将讨论利用过渡金属催化,通过单个氮原子插入来获得含氮杂环的骨架编辑这一迅速发展的领域,重点是各种碳环的氮插入。
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引用次数: 0
Recent Advances in Thermally Activated Delayed Fluorescent Materials in Type II Photodynamic Therapy 第二类光动力疗法中热激活延迟荧光材料的最新进展。
IF 7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-26 DOI: 10.1002/tcr.202400146
Jônatas F. Berbigier, Lilian C. da Luz, Fabiano S. Rodembusch

Photodynamic therapy (PDT) represents a novel, dual-stage cancer treatment approach that combines light energy and photosensitizers to destroy cancerous and precancerous cells through the generation of radicals (Type I) or singlet oxygen (Type II). Since the early 2010s, PDT has advanced significantly, with the focus shifting toward the exploration of molecules capable of thermally activated delayed fluorescence (TADF) as viable alternatives to traditional metallic complexes and organometallic compounds for producing the necessary active species. TADF molecules exhibit higher energy conversion efficiency, long-lived triplet excitons, tunable photophysical properties, and a small singlet-triplet energy gap, facilitating efficient intersystem crossing and enhanced singlet oxygen generation. As metal-free luminophores, they offer benefits such as reduced health risks, high structural flexibility, and biocompatibility, which can significantly enhance PDT treatment efficacy. Notably, in 2019, a pivotal shift occurred, with researchers concentrating their efforts on identifying and investing in potential molecules specifically for Type II PDT applications. This review presents the innovative use of materials characterized by closely spaced S1 and T1 orbitals, crucial for the efficient generation of singlet oxygen in PDT. Exploring these materials opens new avenues for enhancing the efficacy and specificity of PDT, offering promising for future cancer treatments.

光动力疗法(PDT)是一种新型的双阶段癌症治疗方法,它结合了光能和光敏剂,通过产生自由基(I 型)或单线态氧(II 型)来破坏癌细胞和癌前病变细胞。自 2010 年代初以来,PDT 取得了长足的进步,重点转向探索能够产生热激活延迟荧光(TADF)的分子,以此替代传统的金属络合物和有机金属化合物来产生必要的活性物质。热激活延迟荧光分子具有更高的能量转换效率、长寿命的三重激子、可调的光物理特性以及较小的单线-三重能隙,有利于高效的系统间交叉和增强单线态氧的生成。作为不含金属的发光体,它们具有降低健康风险、结构灵活性高和生物相容性好等优点,可显著提高 PDT 治疗效果。值得注意的是,2019 年发生了关键性的转变,研究人员集中精力鉴定和投资专门用于 II 型 PDT 应用的潜在分子。本综述介绍了以紧密间隔的 S1 和 T1 轨道为特征的材料的创新应用,这些材料对于在 PDT 中高效生成单线态氧至关重要。探索这些材料开辟了提高光导疗法疗效和特异性的新途径,为未来的癌症治疗带来了希望。
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引用次数: 0
Recent Advances in Selenium-Mediated Redox Functional Group Interconversions 硒介导的氧化还原官能团相互转化的最新进展。
IF 7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-22 DOI: 10.1002/tcr.202400174
Antonella Capperucci, Damiano Tanini

The conversion of a functional group into another represents the core of organic synthesis. Within the arena of functional group interconversions, oxidative and reductive transformations occupy a privileged position and the development of new sustainable, selective, and general methodologies continue to attract significant interest. Owing to the versatility of their chemistry, selenium compounds offer significant opportunities to achieve both oxidation and reduction of a wide range of functional groups. Additionally, the possibility to generate in situ the active oxidant or reducing selenium species from suitable inert precursors enables the development of catalytic processes. In this review, recent advances in selenium-mediated oxidative and reductive functional group interconversions, with particular emphasis on cutting-edge researches bringing about new insights into the comprehension of their mechanistic aspects, will be discussed.

将一个官能团转化为另一个官能团是有机合成的核心。在官能团相互转化的领域中,氧化和还原转化占据着重要地位,开发新的可持续、选择性和通用方法继续吸引着人们的极大兴趣。由于硒化合物化学性质的多样性,它为实现多种官能团的氧化和还原提供了重要机会。此外,从合适的惰性前体中原位生成活性氧化剂或还原硒物种的可能性也使得催化过程的开发成为可能。在这篇综述中,将讨论硒介导的氧化和还原官能团相互转化的最新进展,特别强调为理解其机理方面带来新见解的前沿研究。
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引用次数: 0
Recent Progress in Steroid C(sp3)−H Functionalization 类固醇 C(sp3)-H 官能化的最新进展。
IF 7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-20 DOI: 10.1002/tcr.202400150
Agnieszka Wojtkielewicz, Adam D. Majewski, Zenon Łotowski

Selective C−H functionalization methods could provide a valuable tool for synthesizing different steroid derivatives, which is essential not only in contexts of developing novel synthetic methodology but also as a direct way for gathering the analogues needed for studying the structure-activity relationships and obtaining biologically active compounds. The review discusses recent examples of steroid C−H functionalization to various C−X derivatives (C−O, C−C, C−N, C−S, and C−halogen) using available methods emphasizing their scope and limitations.

选择性 C-H 功能化方法可以为合成不同的类固醇衍生物提供有价值的工具,这不仅对开发新的合成方法至关重要,而且也是收集研究结构-活性关系和获得生物活性化合物所需的类似物的直接途径。本综述讨论了利用现有方法将类固醇 C-H 功能化为各种 C-X 衍生物(C-O、C-C、C-N、C-S 和 C-卤素)的最新实例,强调了这些方法的范围和局限性。
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引用次数: 0
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