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Catalytic oligomerization and polymerization of ethylene with complexes of iron triad metals: influence of metal nature and new prospects 铁三元金属配合物催化乙烯的低聚聚合:金属性质的影响及新前景
IF 7.7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2021-01-01 DOI: 10.1070/RCR5021
S. Zubkevich, V. Tuskaev, S. Gagieva, B. Bulychev
In the last five years the field of catalytic oligomerization and polymerization of olefins using complexes of late transition metals has been the most intensively developing area of post-metallocene catalysis. This review is devoted to detailed analysis of the influence of metal nature on the catalytic properties of systems based on complexes of iron triad metals. Some novel and developing areas of application of such complexes in olefin oligomerization and polymerization (ethylene trimerization, production of olefins with an odd number of carbon atoms and polyethylene waxes, targeted synthesis of heavy fractions of ethylene oligomers) are surveyed. Different approaches to the heterogenization of catalysts on various solid supports are considered. The bibliography includes 225 references.
近五年来,利用后过渡金属络合物催化烯烃的低聚和聚合已成为茂金属后催化领域发展最为迅速的领域。本文详细分析了金属性质对铁三元配合物体系催化性能的影响。综述了该类配合物在烯烃低聚和聚合(乙烯三聚、奇数碳原子烯烃和聚乙烯蜡的生产、乙烯低聚物重馏分的定向合成)中的一些新的和有发展前途的应用领域。考虑了催化剂在不同固体载体上异质化的不同方法。参考书目包括225篇参考文献。
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引用次数: 3
Recent advances in computational liquid-phase 77Se NMR 计算液相77Se核磁共振的最新进展
IF 7.7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2021-01-01 DOI: 10.1070/RCR4960
L. Krivdin
This review aims to highlight significant progress in the calculation of 77Se NMR chemical shifts and spin – spin coupling constants involving selenium substantiated with a vast amount of experimental data. The material is arranged in two basic sections: the first one dealing with the calculation of 77Se NMR chemical shifts and the second one dealing with the computation of spin – spin coupling constants involving 77Se nucleus, namely 77Se–1H, 77Se–13C and 77Se–77Se together with some more exotic types of couplings, 77Se – 15N, 77Se–19F, 77Se–29Si and 77Se–31P. A special attention is focused on the stereoelectronic effects involving selenium atom and their manifestation in the 77Se NMR spectra of organoselenium compounds studied with the aid of the modern calculation of 77Se NMR parametres in combination with experimental results. The bibliography includes 114 references.
本文综述了77Se核磁共振化学位移和包含硒的自旋-自旋耦合常数计算的重大进展,并得到了大量实验数据的证实。材料被安排在两个基本部分:第一部分计算77Se核磁共振化学位移,第二部分计算涉及77Se核的自旋-自旋耦合常数,即77Se - 1h, 77Se - 13c和77Se - 77Se,以及一些更奇特的耦合类型,77Se - 15N, 77Se - 19f, 77Se - 29si和77Se - 31p。利用现代计算方法,结合实验结果,研究了有机硒化合物的77Se核磁共振谱中涉及硒原子的立体电子效应及其表现。参考书目包括114篇参考文献。
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引用次数: 5
Computational NMR of heavy nuclei involving 109Ag, 113Cd, 119Sn, 125Te, 195Pt, 199Hg, 205Tl, and 207Pb 109Ag、113Cd、119Sn、125Te、195Pt、199Hg、205Tl和207Pb重核的计算核磁共振
IF 7.7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2021-01-01 DOI: 10.1070/RCR4976
L. Krivdin
The present review addresses the computation of the NMR parameters of 109Ag, 113Cd, 119Sn, 125Te, 195Pt, 199Hg, 205Tl, and 207Pb isotopes. The presented material is based on papers that appeared mainly in the interim period of 2000–2020. These calculations are rapidly developing and becoming of increasing practical interest on the cutting edge of modern computational chemistry. The review focuses on the most essential papers in this area, concentrating on the computational aspects of such calculations together with their structural and stereochemical applications in organometallic chemistry, which seems to be urgent and timely. The bibliography includes 173 references.
本文讨论了109Ag、113Cd、119Sn、125Te、195Pt、199Hg、205Tl和207Pb同位素核磁共振参数的计算。所呈现的材料是基于论文,主要出现在2000-2020年的过渡时期。这些计算正在迅速发展,并在现代计算化学的前沿日益引起人们的实际兴趣。这篇综述集中在这一领域最重要的论文,集中在这类计算的计算方面,以及它们在有机金属化学中的结构和立体化学应用,这似乎是迫切和及时的。参考书目包括173篇参考文献。
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引用次数: 3
Electrode materials based on complex d-metal oxides for symmetrical solid oxide fuel cells 对称固体氧化物燃料电池的复合d-金属氧化物电极材料
IF 7.7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2021-01-01 DOI: 10.1070/RCR4979
S. Istomin, N. Lyskov, G. Mazo, E. Antipov
The review addresses and highlights the main results of research on the physicohemical properties of single-phase and composite materials based on transition metal oxides in relation to their practical application as electrode materials for symmetrical solid oxide fuel cells. The electronic structures and thermodynamic stability of transition metal oxides with the perovskite structure are discussed. A detailed consideration is given to the thermal behaviour, chemical stability, electrical conductivity and electrochemical properties of a broad range of electrode materials based on iron-, chromium- and manganese-containing perovskite-like oxides and oxides that crystallize in other structure types. The analysis revealed the most promising compositions of electrode materials for symmetrical solid oxide fuel cells and effective approaches to the improvement of their functional characteristics. The bibliography includes 202 references.
综述了基于过渡金属氧化物的单相和复合材料的物理化学性质及其作为对称固体氧化物燃料电池电极材料的实际应用方面的主要研究成果。讨论了具有钙钛矿结构的过渡金属氧化物的电子结构和热力学稳定性。详细考虑了基于含铁,含铬和含锰的钙钛矿类氧化物和以其他结构类型结晶的氧化物的广泛电极材料的热行为,化学稳定性,电导率和电化学性能。分析结果揭示了对称固体氧化物燃料电池电极材料最有前途的组成和改善其功能特性的有效途径。参考书目包括202篇参考文献。
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引用次数: 21
Matrix isolation in laboratory astrochemistry: state-of-the-art, implications and perspective 实验室天体化学中的基质分离:最新技术、意义和前景
IF 7.7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2021-01-01 DOI: 10.1070/RCR4995
V. Feldman, S. Ryazantsev, S. Kameneva
Recent progress in observational astronomy and astrophysics has stimulated intensive laboratory studies aimed at elucidating the mechanisms of evolution of molecular matter in interstellar space and various space objects. One of the most intriguing and rapidly developing areas of these studies is the so-called “cold astrochemistry” devoted to the complex processes occurring in astrophysical ices. In this context, the matrix isolation technique (known for decades) is a very useful approach for both interpreting the results of astrophysical observations and verifying possible mechanisms of key astrochemical processes. This review outlines the most important results of recent studies using the matrix isolation technique. In fact, the results of these studies contribute to “cold” astrochemistry in two main aspects: (i) spectroscopy of astrochemically important molecules, ions and radicals stabilized in cryogenic matrices; (ii) experimental modeling of mechanisms of radiation-induced and “in dark” chemical reactions occurring in “cold” space environments (interstellar, cometary and planetary ices). In the first aspect, special attention is paid to new spectroscopic data obtained using various methods (electronic and vibrational absorption spectroscopy, electron paramagnetic resonance spectroscopy). In the second aspect, we consider the chemical effects resulting from both direct excitation of isolated molecules and the transfer of energy initially absorbed by the medium. Special attention has been paid to recent studies of spectroscopic characteristics and radiation-induced evolution of matrix-isolated weak intermolecular complexes, which can be considered “building blocks” for cold synthesis of complex molecules in the absence of diffusion mobility. In addition, we consider the use of matrix isolation for the studies of low-temperature chemical reactions “in dark” involving atoms and highly reactive intermediates, which can occur in cold space environments. In the final part, we briefly discuss the applicability of the results of matrix isolation experiments for interpretation of the mechanisms in molecular ices and highlight the prospects of this field. The review can also be useful for specialists in various aspects of chemistry and chemical physics (radiation chemistry, photochemistry, molecular spectroscopy, low-temperature chemistry). The bibliography includes 379 references.
观测天文学和天体物理学的最新进展刺激了旨在阐明星际空间和各种空间物体中分子物质演化机制的密集实验室研究。这些研究中最有趣和发展最快的领域之一是所谓的“冷天体化学”,它致力于研究天体物理冰中发生的复杂过程。在这种情况下,基质分离技术(几十年来众所周知)是解释天体物理观测结果和验证关键天体化学过程可能机制的一种非常有用的方法。本文综述了近年来利用基质分离技术研究的最重要结果。事实上,这些研究的结果在两个主要方面为“冷”天体化学做出了贡献:(i)在低温基质中稳定的天体化学重要分子、离子和自由基的光谱学;㈡对在"冷"空间环境(星际冰、彗星冰和行星冰)中发生的辐射诱导和"黑暗中"化学反应机制进行实验模拟。在第一个方面,特别关注使用各种方法(电子和振动吸收光谱,电子顺磁共振光谱)获得的新的光谱数据。在第二个方面,我们考虑了孤立分子的直接激发和介质最初吸收的能量转移所产生的化学效应。近年来,人们特别关注基质分离的弱分子间配合物的光谱特征和辐射诱导演化的研究,这些弱分子间配合物可以被认为是在没有扩散迁移率的情况下冷合成复杂分子的“基石”。此外,我们考虑使用基质分离来研究“在黑暗中”涉及原子和高活性中间体的低温化学反应,这可能发生在寒冷的空间环境中。最后,我们简要讨论了基质分离实验结果在解释分子冰机制方面的适用性,并对该领域的发展前景进行了展望。本综述对化学和化学物理(辐射化学、光化学、分子光谱学、低温化学)各方面的专家也很有用。参考书目包括379篇参考文献。
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引用次数: 3
Chemical micro-oscillators based on the Belousov–Zhabotinsky reaction 基于Belousov-Zhabotinsky反应的化学微振荡器
IF 7.7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2021-01-01 DOI: 10.1070/RCR5009
Ilya L. Mallphanov, V. Vanag
The results of studies on the development of micro-oscillators (MOs) based on the Belousov –Zhabotinsky (BZ) oscillatory chemical reaction are integrated and systematized. The mechanisms of the BZ reaction and the methods of immobilization of the catalyst of the BZ reaction in micro-volumes are briefly discussed. Methods for creating BZ MOs based on water microdroplets in the oil phase and organic and inorganic polymer microspheres are considered. Methods of control and management of the dynamics of BZ MO networks are described, including methods of MO synchronization. The prospects for the design of neural networks of MOs with intelligent-like behaviour are outlined. Such networks present a new area of nonlinear chemistry, including, in particular, the creation of a chemical ‘computer’. The bibliography includes 250 references.
对基于别洛乌索夫-扎博廷斯基(Belousov -Zhabotinsky, BZ)振荡化学反应的微振荡器(MOs)的研究成果进行了整合和系统化。简要讨论了BZ反应的机理和BZ反应催化剂的微体积固定化方法。研究了基于油相水微滴和有机、无机聚合物微球制备BZ MOs的方法。介绍了BZ MO网络的动态控制和管理方法,包括MO同步方法。展望了具有类智能行为的MOs神经网络设计的前景。这样的网络呈现出非线性化学的一个新领域,特别是包括化学“计算机”的创造。参考书目包括250篇参考文献。
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引用次数: 2
Solid oxide fuel cells based on ceramic membranes with mixed conductivity: improving efficiency 混合导电性陶瓷膜固体氧化物燃料电池:提高效率
IF 7.7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2021-01-01 DOI: 10.1070/RCR4966
E. Pikalova, E. Kalinina
Modern approaches to increasing the efficiency of solid-oxide fuel cells (SOFCs) based on electrolytic membranes with mixed conductivity are considered. These approaches are based on material-science concepts (expansion of the electrolytic domain boundary due to the doping of basic oxides and development of various composite materials) and various technological solutions (application of electron-blocking layers on the anode and cathode sides, rational selection of the electrolyte thickness, and optimization of the electrolyte and electrode structures by synthesizing heterostructures). The methods of mathematical modelling of devices with an electrolytic membrane having mixed conductivity are analyzed in order to determine the most efficient design and optimal operation conditions for SOFCs. The application of nanocomposite electrolytes with a core – shell structure and salt composites is considered. Data on new design solutions — single-layer and single-chamber SOFCs — are presented. The prospects of the proposed approaches are evaluated. The bibliography includes 384 references.
研究了提高混合电导率电解膜固体氧化物燃料电池(SOFCs)效率的现代方法。这些方法基于材料科学概念(由于碱性氧化物的掺杂和各种复合材料的开发而扩大电解畴边界)和各种技术解决方案(在阳极和阴极侧应用电子阻挡层,合理选择电解质厚度,以及通过合成异质结构来优化电解质和电极结构)。分析了具有混合电导率的电解膜器件的数学建模方法,以确定sofc的最有效设计和最佳运行条件。讨论了核壳结构纳米复合电解质与盐复合材料的应用。介绍了新的设计方案-单层和单室sofc的数据。对所提方法的前景进行了评价。参考书目包括384篇参考文献。
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引用次数: 11
Conjugated nitroxides 共轭硝基氧
IF 7.7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2021-01-01 DOI: 10.1070/rcr5025
E. Tretyakov, V. Ovcharenko, A. Terent’ev, I. Krylov, T. Magdesieva, D. Mazhukin, N. Gritsan
In recent years, research dealing with organic paramagnetic compounds such as stable radicals and high-spin systems has been focused on applied aspects. Several key trends have formed in the application and, hence, in the function-oriented synthesis of organic radicals and polyradicals. This review addresses one of such trends in which the dominant role is played by so-called conjugated nitroxides. Their specific feature is the presence of any unsaturated moiety (C=C, C=N or C=O multiple bond; aromatic or heteroaromatic ring; fused polyaromatic system) adjacent to the nitroxide group. The achievements of the chemistry of conjugated nitroxides are presented, and their physicochemical properties, magneto-structural correlations and practical applications are discussed. The bibliography includes 641 references.
近年来,对稳定自由基和高自旋体系等有机顺磁性化合物的研究主要集中在应用方面。在有机自由基和多自由基的应用和定向合成中形成了几个关键的趋势。这篇综述解决了这样的趋势之一,其中主导作用是发挥所谓的共轭氮氧化物。它们的具体特征是存在任何不饱和基团(C=C, C=N或C=O多键;芳香或杂芳香环;熔融多芳系)与氮氧化物基团相邻。介绍了共轭氮氧化物的化学研究进展,讨论了共轭氮氧化物的物理化学性质、磁结构关系和实际应用。参考书目包括641篇参考文献。
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引用次数: 21
Titanium dioxide nanotubes: synthesis, structure, properties and applications 二氧化钛纳米管:合成、结构、性能及应用
IF 7.7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2021-01-01 DOI: 10.1070/RCR4991
A. Rempel, A. Valeeva, A. Vokhmintsev, I. Weinstein
Methods of synthesis of nanotubular structures based on titania of various phase and chemical compositions are described. A systematic account is given of known data about the influence of synthesis and subsequent treatment conditions on the amorphous and crystal structures, specific surface area, morphology and optical, luminescence and electro-physical properties of titania-based nanotubular oxide materials. The photocatalytic properties in the oxidation reactions of organic compounds and the performance characteristics of the memristive behaviour of TiO2-based nanotubular structures are considered in details. Their applications are discussed. The bibliography includes 238 references.
介绍了不同相、不同化学成分的二氧化钛纳米管结构的合成方法。系统地叙述了合成和后续处理条件对钛基纳米管氧化物材料的非晶和晶体结构、比表面积、形貌、光学、发光和电物理性能的影响。详细讨论了二氧化钛基纳米管结构在有机化合物氧化反应中的光催化性能和忆阻行为的性能特征。讨论了它们的应用。参考书目包括238个参考文献。
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引用次数: 11
Recent advances in chemistry of high-spin nitrenes 高自旋亚硝基烯的化学研究进展
IF 7.7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2021-01-01 DOI: 10.1070/RCR4965
S. Chapyshev, D. Korchagin, E. Y. Misochko
Experimental and theoretical studies on aromatic nitrenes bearing from three to six unpaired electrons and having quartet, quintet, sextet or septet ground spin states, published in the last 15 years are analyzed. A comparative analysis of the magnetic properties of high-spin nitrenes and all other known high-spin organic molecules is performed. Promising areas of practical application of high-spin nitrenes as molecular magnets and as qubits and qudits for quantum computations are discussed. The bibliography includes 214 references.
本文分析了近15年来关于含有3 ~ 6个未配对电子并具有四重奏、五重奏、六重奏或七重奏基态的芳香亚硝基烯的实验和理论研究。比较分析了高自旋亚硝基烯和所有其他已知的高自旋有机分子的磁性能。讨论了高自旋亚硝基烯在分子磁体、量子比特和量子计算中的应用前景。参考书目包括214篇参考文献。
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引用次数: 0
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Russian Chemical Reviews
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