A Collaboration for Guiding the Rational Design of Multielement Solid Catalysts

This invited Team Profile was created by the Inorganic Chemistry and Catalysis group, Department of Chemistry, University of Utrecht, the Netherlands; X-ray Laboratory, Department of Physics, University of Helsinki, Finland; Laboratory of Inorganic Chemistry, Department of Chemistry and Applied Biosciences, ETH Zürich, Switzerland; Center for Materials Science and Nanotechnology, Department of Physics, University of Oslo, Norway; and Catalysis Research Center, Department of Chemistry, University of Oslo, Norway. They recently published an article on their successfully designed laboratory-based setup enabling operando multi-edge X-ray absorption near-edge structure (XANES), which offers possibilities for advanced catalyst characterization, as demonstrated for mono-, bi-, and trimetallic CO₂ hydrogenation catalysts consisting of Ni, Cu, and Fe. Synergistic effects during catalyst reduction and their influence on catalytic performance were unravelled, guiding rational design of multielement solid catalysts for various applications. “Operando Laboratory-based Multi-edge X-ray Absorption Near-Edge Spectroscopy of Solid Catalysts”, N. S. Genz, A.-J. Kallio, R. Oord, F. Krumeich, A. Pokle, Ø. Prytz, U. Olsbye, F. Meirer, S. Huotari, B. M. Weckhuysen, Angew. Chem. Int. Ed. 2022, e202209334 ; Angew. Chem. 2022, e202209334 .     

NaY沸石超笼中合成12-钼磷杂多酸

针对负载杂多酸催化剂在极性反应体系中活性组分易溶脱的难题, 用“瓶中造船(ship in the bottle)”的方法在NaY沸石超笼中合成了12-钼磷酸. 将机械混和的MoO₃晶体和NaY沸石在高温下焙烧, 使MoO₃在沸石表面高度分散, 以此复合物在磷酸水溶液中反应, 得到的固体样品用X射线衍射仪(XRD)、³¹P核磁共振谱(³¹P NMR)和红外光谱(IR)进行了表征, 并测试了其在醋酸和正丁醇的酯化反应中的催化性能. 结果表明, MoO₃质量分数为10%的MoO₃/NaY 中载体仍保持Y沸石的结构, 以此为原料合成的样品呈现出Keggin结构杂多酸的红外特征峰, 并且在核磁共振磷谱中杂多酸的化学位移峰向负值方向发生了较大程度的位移, 说明杂多阴离子与Y沸石羟基发生了强相互作用, 样品在醋酸与正丁醇的酯化反应中显示出了较高的催化活性和优异的重复使用性能. 这些充分说明在NaY沸石超笼中成功合成了12-钼磷酸.     

Synthesis and anti-HIV-1 activity of S-dihydro(alkyloxy)benzyloxypyrimidine derivatives

Several 2-heteroaryl-, 2-heteroarylcarbonylmethyl-, 2-arylcarbonylmethyl, and 2-arylethyl derivatives of S-dihydro(alkyloxy)benzyloxypyrimidines have been synthesized and the anti-HIV activities of these compounds were tested in C8166 cell and against RT enzyme. It was found that some of these compounds showed good activity against HIV-1 (EC ₅₀ = 0.014–0.8 μM) with low toxicity (CC ₅₀ value of 222–564 μM) and high selectivity (SI value of 278–37743). The structure-activity relationships (SAR) of these compounds have also been discussed. First two authors contributed equally to this work Correspondence: Yan-Ping He, Key Laboratory of Medicinal Chemistry for Natural Resource Ministry of Education, School of Chemical Science and Technology, Yunnan University, Kunming 650091, People’s Republic of China; Yong-Tang Zheng, Laboratory of Molecular Immunopharmacology, Key Laboratory of Animal Models and Human Disease Mechanisms, Chinese Academy of Sciences, Kunming Institute of Zoology, Kunming, Yunnan 650223, People’s Republic of China.     

《电化学分析传感》专辑序言

《电化学分析传感》专辑序言 电化学分析传感是一种基于界面电荷相互作用的测量方法,具有高灵敏、响应快、无标记等本征优势. 该方法的核心思路是将待测对象构建成为化学电池的某一部分,通过测量界面电子转移或电荷重排过程中产生的电信号响应,如电池电位、电流、电导、电量变化,对待测目标进行定性定量动态地检测、监测或表征. 　　近年来,伴随着测量仪器性能和数据处理方法的持续提高与优化,电化学分析传感研究前沿热点越来越多地关注到纳米尺度界面上的瞬态电荷相互作用、动态电荷传输机制,特别是发展限域空间内的单体纳米电化学信号放大、传输、记录、解析新模式和新策略. 其中,单体电化学分析,如单颗粒碰撞法等,不仅可以得到常规宏观测量的单一平均结果,同时还能描绘出所有不同颗粒结构与性能的完整分布,揭示少量但关键的电化学活性位点和反应机理;而纳米限域电化学分析,如纳米孔道协同测量等,则能通过限域效应有效延长亚稳态中间体的结构寿命,灵敏识别不同待测单体间的细微理化性质差异及其动态变化过程. 此外,电分析方法也更多地与谱学、成像等技术联用,对界面电化学过程进行原位、实时、在线表征,以期揭示纳米界面的电荷传递和能量转化的化学本质. 进而指导设计构建高灵敏电化学传感器,实现在疾病的早期检测、能源转换的高效率用、水体环境污染的有效治理等国家战略性产业中的广泛应用. 　　本专辑围绕电化学分析传感新方法与新技术,收录了在相关研究领域具有丰富经验积累和影响力的团队所撰写的21篇相关研究进展的综述文章和研究论文（分成两期出版,分别包含10篇和11篇）. 希望借助此专辑的出版,能使广大读者更好地了解当前电化学测量领域的研究现状、研究趋势和存在的问题及挑战,推动我国下一代电化学精准分析技术和高效传感应用的进一步发展. 　　最后,对本专辑的所有作者、审稿人及编辑部工作人员的辛勤工作和付出表示由衷的感谢！     

An imidazolium tosylate salt as efficient and recyclable catalyst for acetylation in an ionic liquid

A novel non-metallic salt, 1-butyl-3-methylimidazolium tosylate ([bmim][OTs]) dissolved in the ambient temperature ionic liquid of 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄]), was found to be the efficient catalyst for acetylation with the advantages of good recyclability, avoidance of metal contamination, mild reaction conditions, and wide availability for substrates (alcohols, phenols, and amines), could completely replace organic bases, metal Lewis acids, or metallic triflates to fulfill acetylation by a nucleophilic catalytic mechanism, which was supported by ¹³C NMR analysis. Correspondence: Ye Liu, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Chemistry Department of East China Normal University, Shanghai 200062, China.     

A Japan–Poland Collaboration for Coupling Molecular Nanomagnetism and Luminescent Thermometry

This invited Team Profile was created by the Laboratory of Advanced Functional Materials (Tokoro Lab), Division of Materials Science, Faculty of Pure and Applied Sciences, University of Tsukuba (Japan) ; the Multifunctional Luminescent Materials Group (Szymon Group, MLMG), Faculty of Chemistry, Jagiellonian University, Kraków (Poland) ; and the Solid State Physical Chemistry Group (Ohkoshi Lab), Department of Chemistry, School of Science, The University of Tokyo (Japan) . They recently published an article on a bimetallic cyanido-bridged Tb^III−Co^III framework exhibiting a desolvation-induced structural transformation providing high-symmetry trigonal-prismatic [Tb^III(NC)₆]³⁻ complexes. This induces a strong magnetic anisotropy leading to single-molecule magnet behavior with an energy barrier of 854(26) K, which appears in the cryogenic temperatures range, together with the concomitant luminescent thermometry effect. “Desolvation-Induced Highly Symmetrical Terbium(III) Single-Molecule Magnet Exhibiting Luminescent Self-Monitoring of Temperature”, J. Wang, J. J. Zakrzewski, M. Zychowicz, Y. Xin, H. Tokoro, S. Chorazy, S. Ohkoshi, Angew. Chem. Int. Ed. 2023, 62, e202306372 .     

Titrimetric analysis of total mercury ions including mercury(I) ions

A systematic analytical method is proposed and applied to directly determine the total concentration of Hg(II) and Hg(I) ions in water. Experimental results demonstrate that this method provides a low detection limit of 0.05 mM and small relative error within 1.5% in an ion concentration range of 0.2–50 mM. The technique is especially applicable for sample solutions that the traditional titration method like Volhard and EDTA complexation titrimetry could not analyze directly. This method could be employed to analyze solutions in any ratio of Hg(II) and Hg(I) ions including pure Hg(II) or pure Hg(I) ions, exhibiting several advantages, such as simple operation, good reproducibility, and low cost. Correspondence: Xin-Gui Li, Key Laboratory of Advanced Civil Engineering Materials, Institute of Materials Chemistry, College of Materials Science and Engineering, Tongji University, 1239 Siping Road, Shanghai 200092, China.     

花球状二硫化钒的制备及其储锂研究

采用一步水热法并添加表面活性剂聚乙二醇400制备出花球状二硫化钒,利用X射线粉末衍射仪、场发射扫描电子显微镜等方法对产物的物相和形貌进行了表征. 观测生长过程发现花球状二硫化钒由若干六边形二硫化钒纳米片堆叠穿插组成,该花球状结构使材料拥有较高的比表面积及出色的结构稳定性. 将花球状二硫化钒用于锂离子电池正极材料测试,结果表明花球状二硫化钒在电压区间为1 ~ 3 V,电流密度为200 mA·g^-1时具有出色的循环稳定性且循环50周之后容量可达450 mAh·g^-1.     

Triethylammonium acetate (TEAA): a recyclable inexpensive ionic liquid promotes the chemoselective aza- and thia-Michael reactions

A new, highly efficient, inexpensive, recyclable, mild, convenient, and green protocol for chemoselective aza/thia-Michael addition reactions of amines/thiols to α,β-unsaturated compounds using triethylammonium acetate (TEAA) ionic liquid was developed. The catalyst can be recycled ten times and obviate the need for toxic and expensive catalysts. Correspondence: Akhilesh K. Verma, Green Organic Chemistry Research Laboratory, Dr. B.R. Ambedkar Center for Biomedical Research, University of Delhi, Delhi 110007, India.     

In situ spectroelectrochemical behaviour of nanocrystalline TiO2 thin films electrode fabricated by pulsed laser deposition

Nanocrystalline titanium oxide thin films have been successfully deposited on IT0 coated glass by pulsed laser ablation of metallic Ti target in 0₃/0₂ ambient gases. The intercalation of Li ions in the anatase TiO₂ film electrode is examined by cyclic voltammetry. The electrochromic behaviour of TiO₂ electrode is investigated byin-situ visible transmittance measurement, and two absorption bands at 420 and 650 nm are observed. The absorption falling and rising in color changing with excellent revisibility is relative to the insertion and deintercalation processes of Li ion. These results suggest that nanocrystalline titanium oxide films fabricated by pulsed laser deposition exhibit excellent spectroelectrochemical property. Project supported by the National Natural Science Foundation of China (Grant No. 29783001) and State Key Laboratory for Physical Chemistry of Solid Surface of Xiamen University (1997).     

基于热控电极的电致化学发光传感器的研究进展

电致化学发光（ECL）检测技术因其具有无需激发光源、仪器简单、灵敏度高、选择性好等特点,被广泛应用于环境分析、生物分析等领域. 温度是影响ECL的主要因素之一,在传统的ECL传感器中大多是通过溶液整体加热的方法来控制温度,这种方法操作繁琐,且溶液中的热不稳定性物质及易挥发性物质容易受到影响,因此电极很少工作在最适宜的温度下. 热控电极技术可以只提高电极表面温度,而维持溶液的整体温度不变,使用起来具有很好的便利性. 作者课题组首次将热控电极引入到ECL传感器的构建中,由于电极表面和溶液之间存在一定的温度梯度,因此可以引发强制对流,从而加快物质的扩散和对流速率;电极表面温度的升高还可以进一步提高电极表面物质的电化学反应速率,这两方面的共同作用提高了ECL检测的灵敏度. 同时,利用热控电极可以解决整体加热所引起的背景信号升高,挥发性、热不稳定性物质易受温度影响等问题,而且通过电极加热的方法可去除电极表面的污染物,从而提高ECL检测的重现性. 本文综述了近年来基于热控电极技术的ECL传感器的研究进展,主要介绍了热控电极的加热方式、电极种类以及热控电极在ECL中的应用等,并分析了该技术在实际应用中面临的主要问题,对该技术未来的发展趋势进行了展望.     

Reaction Dynamics in Extreme Environments and Astrochemistry

Ralf I. Kaiser is Professor of Physical Chemistry at the Department of Chemistry and Director of the W.M. Keck Laboratory in Astrochemistry, Department of Chemistry, University of Hawaii at Manoa (USA). He is a current member of the ChemPhysChem Editorial Board.     

Surface Chemistry and Catalytic Reactivity of Borocarbonitride in Oxidative Dehydrogenation of Propane

Borocarbonitride (BCN) materials are newly developed oxidative dehydrogenation catalysts that can efficiently convert alkanes to alkenes. However, BCN materials tend to form bulky B₂O₃ due to over-oxidation at the high reaction temperature, resulting in significant deactivation. Here, we report a series of super stable BCN nanosheets for the oxidative dehydrogenation of propane (ODHP) reaction. The catalytic performance of the BCN nanosheets can be easily regulated by changing the guanine dosage. The control experiment and structural characterization indicate that the introduction of a suitable amount of carbon could prevent the formation of excessive B₂O₃ from BCN materials and maintain the 2D skeleton at a high temperature of 520 °C. The best-performing catalyst BCN exhibits 81.9 % selectivity towards olefins with a stable propane conversion of 35.8 %, and the propene productivity reaches 16.2 mmol h⁻¹ g⁻¹, which is much better than hexagonal BN (h-BN) catalysts. Density functional theory calculation results show that the presence of dispersed rather than aggregated carbon atoms can significantly affect the electronic microenvironment of h-BN, thereby boosting the catalytic activity of BCN.     

二维多层状Ti3C2Tx-MXene/聚吡咯纳米线复合材料的制备及电容性能研究

本文以体相材料MAX(Ti₃AlC₂)为基底,采用氢氟酸刻蚀法得到二维多层状Ti₃C₂T_x-MXene,将一维聚吡咯纳米线(polypyrrole nanowires,PPy-NW)与二维多层状Ti₃C₂T_x-MXene相结合,成功地制备出Ti₃C₂T_x-MXene/PPy-NW复合电极材料. 并分别利用扫描电子显微镜(scanning electron microscope,SEM)、X-射线衍射(X-ray diffraction,XRD)、傅里叶变换红外光谱(fourier transform infrared spectroscopy,FTIR)及X射线光电子能谱 (X-ray photoelectron spectroscopy,XPS)对其进行了形貌和结构表征. 最后通过电化学测试表明,二维多层状Ti₃C₂T_x-MXene/PPy-NW复合电极材料在扫描速率为10 mV·s^-1时比电容可达374 F·g^-1,高于纯PPy-NW（304 F·g^-1）,当扫描速率增加至200 mV·s^-1时,仍可保留原比电容值的72.4%,展现出良好的倍率性能. 而且在电流密度为5 A·g^-1下经过2000次的循环伏安实验,其电容保持率可达91.6%,具有良好的循环稳定性. 总之,二维多层状Ti₃C₂T_x-MXene和一维PPy-NW的复合有效地提升了电极材料的电容性能,在电化学能源储存方面有着巨大的应用前景.     

The <Emphasis Type="Italic">Knoevenagel</Emphasis> reaction in water catalyzed by zwitterionic liquids

Three hydroxyl functionalized zwitterionic liquids (ZILs) were found to be novel recyclable catalysts for the Knoevenagel condensation between aldehydes or ketones and active methylene compounds in aqueous medium. Both aldehydes and ketones gave satisfactory results. The products could simply be separated from the catalysts/water, and the catalysts could be recycled six times without noticeably decreasing the catalytic activity. Correspondence: Dong Fang, Jiangsu Provincial Key Laboratory of Coast Wetland Bioresource and Environment Protection, Yancheng Teachers College, 50 Kai Fang Da Dao, Yancheng 224002, Jiangsu, P.R. China.     

A facile one-pot synthesis and the crystal structure of a molecular clip derived from diphenylglycoluril

A facile procedure for the one-pot synthesis of a clip molecule via condensation of diphenylglycoluril, paraformaldehyde, and 4-dimethoxybenzene in the presence of methanesulfonic acid is described. The advantages of this method are mild conditions, single product formation and good yield. Especially, the procedure of the product purification is more simple and convenient. In addition, the clip molecule is characterized by X-ray crystal structure analysis, which shows different weak interactions forces compared to the structure reported previously. Correspondence: Zhi-Guo Wang, Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, Chemistry Department of Central China Normal University, Wuhan 430079, China.     

Quantum dynamics of dissociative adsorption of H2 on Ni(100) using the dynamical Lie algebraic method

A dynamical Lie algebraic method has been applied to treating the quantum dynamics of dissociative adsorption of H₂ on a static flat metal surface. An LEPS potential energy surface has been used to describe the interaction of H₂ with Ni(100) surface. The dependence of the initial state-selected dissociation probability was obtained analytically on the initial kinetic energy and time. A comparison with other theoretical calculations and experiments is made. The results show that the method can be effectively used to describe the dynamics of reactive gas-sdace scattering. Project supported by the National Natural Science Foundation of China (Grant No. 19694033) and partially by the State Key Laboratory of Theoretical and Computational Chemistry of Jilin University (Grant No. 9801).     

Determination of trace vanadium in soil by cloud point extraction and graphite furnace atomic absorption spectroscopy

This work describes a new analytical procedure for trace vanadium by graphite furnace atomic absorption spectroscopy coupled to cloud point extraction (CPE) as the separation-preconcentration method. The CPE behavior of vanadium using methylene blue as complex agent and Triton X-100 as a surfactant was investigated systematically. Under the optimized conditions, the detection limit was 0.7 ng · mL⁻¹, and the relative standard deviation was 4.3% for vanadium (c = 50.0 ng · mL⁻¹, n = 5). The recovery of vanadium was in the range of 98.9–102.8%. The method was applied to the analysis of vanadium in certified reference materials and real samples. The results obtained were in good agreement with the certified values. Correspondence: Xiashi Zhu, Key Laboratory of Environmental Material and Environmental Engineering of Jiangsu province/College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, P.R. China     

New Chiral N,S-Ligands with Thiophenyl at Benzylic Position. Palladium(II)-catalyzed Enantioselective Allylic Alkylation

Ｃｈｉｒａｌｌｉｇａｎｄｓｐｌａｙａｃｒｕｃｉａｌｒｏｌｅｉｎａｓｙｍｍｅｔｒｉｃｃａｔａｌｙｓｉｓ .Ｔｏｄａｔｅａｖａｒｉｅｔｙｏｆｌｉｇａｎｄｓｈａｖｅｂｅｅｎｓｙｎｔｈｅ ｓｉｚｅｄａｎｄｐｒｏｖｅｄｔｏｂｅｅｆｆｅｃｔｉｖｅ .Ａｍｏｎｇｔｈｅｍｔｈｅｌｉｇａｎｄｓ1ｗｉｔｈｂｏｔｈｃｏｏｒｄｉｎａｔｅａｔｏｍｓａｔｂｅｎｚｅｎｅｒｉｎｇ ｐｏｓｉｔｉｏｎｓｓｈｏｗｇｏｏｄｔｏｅｘｃｅｌｌｅｎｔａｓｙｍｍｅｔｒｉｃｉｎｄｕｃｔｉｏｎｉｎｃａｔａｌｙｔｉｃａｓｙｍｍｅｔｒｉｃｒｅａｃｔｉｏｎｓ …     

Quantum dynamics of dissociative adsorption of H2 and D2: The time-dependent wave packet method

A time-dependent quantum wave packet method was used to study the dynamics of dissociative adsorption of H₂ and D₂ on a flat and static surface. The molecule-surface interaction is described using a modified London-Eyring-Polanyi-Sato (LEPS) type potential for the H₂/Ni(100) system. The three-dimensional (3-D) dissociation probabilities were calculated for different initial rovibrational states as a function of initial incident energies. Our results show that the dissociation of the diatomic rotational states whose quantum numbers satisfyj+m = odd is forbidden at low energies for the homonuclear H_z and D₂ due to the selection rule. The effect of the rotational orientation of diatoms on adsorption predicts that the in-plane rotation (m = j) is more favorable for dissociation than the out-of-plane rotation (m = 0). Enhanced dissociation for vibrationally excited molecules and the significant enhancement of the dissociation probability of H2 when compared to D₂ were explained reasonably in terms of quantum mechanical zero-point energies, the tunneling effect and the reflection from an activation barrier. Project supported by the National Natural Science Foundation of China (Grant No. 19694033) and partially by the Science Foundation for Overseas Chinese Scholars and Students, administered by the State Education Commission of China (Grant No. 1992), by the State Key Laboratory of Theoretical and Computational Chemistry of Jilin University at Changchun (Grant No. 98011, and by the Natural Science Foundation of Shandong Province (Grant No. Y96B03022)