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Double [5]carbohelicene: facile synthesis, chiroptical properties,isomerization study, and lasing application

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science China Chemistry 2025年第1期 233-240页

作者： Peipei Liu Yantong Li Meng-Xiang Wu Hao Kang Xiao-Li Zhao Lin Xu Linlin Liu Xiaodong Li Junfeng Fang Zhiwei Fang Ya Cheng Hai-Bo Yang Huakang Yu Xueliang Shi State Key Laboratory of Petroleum Molecular & Process engineering Shanghai Key Laboratory of Green Chemistry and Chemical ProcessesSchool of Chemistry and Molecular Engineering East China Normal University School of Physics and Optoelectronics South China University of Technology Institute of Polymer Optoelectronic Materials & Devices State Key Laboratory of Luminescent Materials & Devices South China University of Technology School of Physics and Electronic science Engineering Research Center of Nanophotonics & Advanced Instrument Ministry of EducationEast China Normal University State Key Laboratory of Precision Spectroscopy School of Physics and Electronic Science East China Normal University

Double carbohelicenes have attracted considerable attention due to their aesthetic structures, distinct π-conjugation extension, inherent chirality, and intriguing optical and electronic properties. Herein, the concise de novo synthesis of a new double[5]carbohelicene 1 together with its chiroptical properties, isomerization process and lasing application is presented. 1 was synthesized by a simple protocol involving the formation of a 6,6′-bipentacene as the key intermediate. It is worth noting that1 existed as two diastereomers 1-PP/MM and 1-PM, which were successfully isolated and unambiguously confirmed by Xray crystallography. The optical resolution of the racemic 1-PP/MM was successfully achieved by chiral-phase highperformance liquid chromatography（HPLC）, and 1-PP and 1-MM were characterized by circular dichroism. Interestingly, it was found that 1-PP/MM could be completely isomerized to 1-PM upon heating, and the detailed thermodynamics and kinetics of the isomerization process were systematically investigated. 1-PM exhibited deep-red luminescence with emission maximum at 723 nm and fluorescence quantum yield as high as 32.95%. Consequently, we can showcase the lasing application of 1-PM by doping with epoxy resin to assemble a bottle microlaser spontaneously, which the lasing wavelength is 796.6 nm at a threshold of 0.8 m J cm-2. We believe that our studies, including the facile synthesis methodology, detailed isomerization studies, and lasing application, will shed some light on the design and synthesis of novel carbohelical systems with more functions.

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Recent progress on photoactive nonprecious transition-metal complexes

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science China Chemistry 2025年第1期 46-95页

作者： Zhong-Liang Gong Hong-Jie Zhang Yan Cheng Jianxun Liu Yuhan Ai Yaqin Li Zhihui Feng Qiong Zhang Shaolong Gong Yong Chen Chang-Jiang Yao Yuan-Yuan Zhu Liang-Jin Xu Yu-Wu Zhong CAS Key Laboratory of Photochemistry Institute of Chemistry Chinese Academy of Sciences State Key Laboratory of Structural Cemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences School of Chemistry and chemical engineering Anhui Key Laboratory of Advanced Catalytic Materials and Reaction EngineeringHefei University of Technology State Key Laboratory of Explosion science and Safety Protection School of Mechatronical Engineering Beijing Institute of Technology College of Chemistry and Molecular sciences Hubei Key Lab on Organic and Polymeric Optoelectronic Materials Wuhan University School of Chemistry and chemical engineering Anhui University Key Laboratory of Photochemical Conversion and Optoelectronic Materials & CAS-HKU Joint Laboratory on New Materials Technical Institute of Physics and Chemistry Chinese Academy of Sciences

Photoactive complexes of nonprecious transition metals, mainly including those in the first-row and partially the second-row of the Periodic table of elements, have received increasing attention in view of their low cost and long-term sustainability. They are recognized as promising alternatives to noble transition metal complex congeners that have been extensively studied in optoelectronic devices, artificial photosynthesis, photocatalysis, biodiagnostics, and therapeutics, etc. This review is devoted to a comprehensive summary on the classical and recent advances on photoactive nonprecious transition metal complexes, including photoactive Zr, V, Cr, Mo, and W complexes, Mn complexes and hybrids, Fe, Co, Ni, and Cu complexes, and Zn and Cd complexes and hybrids. A particular focus is given on the molecular design, modulation of photophysical and photochemical properties, and applications of the representative and lately-developed nonprecious metal complexes. In addition, a perspective on the future development in this field is provided at the end of this review.

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Advancements and Challenges in Organic–Inorganic Composite Solid Electrolytes for All‑Solid‑State Lithium Batteries

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Nano-Micro Letters 2025年第1期17卷 46-97页

作者： Xueyan Zhang Shichao Cheng Chuankai Fu Geping Yin Liguang Wang Yongmin Wu Hua Huo State Key Laboratory of Space Power‑Sources School of Chemistry and Chemical EngineeringHarbin Institute of TechnologyHarbin 150001People’s Republic of China College of chemical and Biological engineering Zhejiang UniversityHangzhou 310058People’s Republic of China State Key Laboratory of Space Power-Sources 2965 Dongchuan RoadMinhang DistrictShanghai 200240People’s Republic of China

To address the limitations of contemporary lithium-ion batteries,particularly their low energy density and safety concerns,all-solid-state lithium batteries equipped with solid-state electrolytes have been identified as an up-and-coming *** the various SEs,organic–inorganic composite solid electrolytes(OICSEs)that combine the advantages of both polymer and inorganic materials demonstrate promising potential for large-scale ***,OICSEs still face many challenges in practical applications,such as low ionic conductivity and poor interfacial stability,which severely limit their *** review provides a comprehensive overview of recent research advancements in ***,the influence of inorganic fillers on the main functional parameters of OICSEs,including ionic conductivity,Li+transfer number,mechanical strength,electrochemical stability,electronic conductivity,and thermal stability are systematically *** lithium-ion conduction mechanism of OICSE is thoroughly analyzed and concluded from the microscopic ***,the classic inorganic filler types,including both inert and active fillers,are categorized with special emphasis on the relationship between inorganic filler structure design and the electrochemical performance of ***,the advanced characterization techniques relevant to OICSEs are summarized,and the challenges and perspectives on the future development of OICSEs are also highlighted for constructing superior ASSLBs.

关键词： Composite solid electrolytes Inorganic filler Interfacial stability Li-ion conduction mechanism Characterization techniques

Spontaneous Orientation Polarization of Anisotropic Equivalent Dipoles Harnessed by Entropy engineering for Ultra‑Thin Electromagnetic Wave Absorber

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Nano-Micro Letters 2025年第1期17卷 424-438页

作者： Honghan Wang Xinyu Xiao Shangru Zhai Chuang Xue Guangping Zheng Deqing Zhang Renchao Che Junye Cheng Liaoning Key Lab of Lignocellulose Chemistry and BioMaterials Liaoning Collaborative Innovation Center for Lignocellulosic BiorefinerySchool of Light Industry and Chemical EngineeringDalian Polytechnic UniversityDalian 116034People’s Republic of China School of Life science and Biotechnology Dalian University of TechnologyDalian 116024People’s Republic of China Department of Mechanical engineering Hong Kong Polytechnic UniversityHung HomKowloonHong Kong 999077People’s Republic of China School of Materials science and engineering Qiqihar UniversityQiqihar 161006People’s Republic of China Laboratory of Advanced Materials Shanghai Key Lab of Molecular Catalysis and Innovative MaterialsAcademy for Engineering&TechnologyFudan UniversityShanghai 200438People’s Republic of China Department of Materials science Shenzhen MSU-BIT UniversityShenzhen 517182People’s Republic of China

The synthesis of carbon supporter/nanoscale high-entropy alloys(HEAs)electromagnetic response composites by carbothermal shock method has been identified as an advanced strategy for the collaborative competition engineering of conductive/dielectric *** migration modes within HEAs as manipulated by the electronegativity,valence electron configurations and molar proportions of constituent elements determine the steady state and efficiency of equivalent ***,enlightened by skin-like effect,a reformative carbothermal shock method using carbonized cellulose paper(CCP)as carbon supporter is used to preserve the oxygencontaining functional groups(O·)of carbonized cellulose fibers(CCF).Nucleation of HEAs and construction of emblematic shell-core CCF/HEAs heterointerfaces are inextricably linked to carbon metabolism induced by O·.Meanwhile,the electron migration mode of switchable electronrich sites promotes the orientation polarization of anisotropic equivalent *** virtue of the reinforcement strategy,CCP/HEAs composite prepared by 35%molar ratio of Mn element(CCP/HEAs-Mn_(2.15))achieves efficient electromagnetic wave(EMW)absorption of−51.35 dB at an ultra-thin thickness of 1.03 *** mechanisms of the resulting dielectric properties of HEAs-based EMW absorbing materials are elucidated by combining theoretical calculations with experimental characterizations,which provide theoretical bases and feasible strategies for the simulation and practical application of electromagnetic functional devices(e.g.,ultra-wideband bandpass filter).

关键词： High-entropy alloys Carbothermal shock Switchable electron migration modes Emblematic shell-core heterointerfaces Ultra-thin thickness

Oxidation of propane to acrylic acid and acetic acid over alkaline earth-doped Mo-V-Sb-O_x catalysts

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Journal of Natural Gas Chemistry 2010年第6期19卷 593-599页

作者： Chandan S.Chaudhari Shailesh S.Sable Hanumant Gurav Ashutosh A.Kelkar Vilas H.Rane chemical engineering and Process Development division National Chemical Laboratory Catalysis division National Chemical Laboratory

Alkaline earth metal （Mg,Ca,Sr and Ba）-doped Mo-V-Sb-O x catalysts,prepared by a dry-up method,have been investigated for their catalytic performance in the oxidation of propane under different reaction *** catalysts have been characterized by N2 adsorption-desorption,temperature-programmed desorption （TPD） of NH3,SEM and *** of water vapor on the catalytic performance,particularly on the selectivities to acetic acid and acrylic acid,has also been *** selectivity to acrylic acid was improved significantly by the doping of alkaline earth metals to Mo-V-Sb-O x *** surface acidic sites of the catalyst decreased with the doping of the catalyst with alkaline earth metals,which ultimately was found to be beneficial for obtaining high selectivity to acrylic *** catalytic activity and product selectivities were found to be influenced by the reaction temperature,C3H8/O2 ratio and space velocity.A significant improvement in the selectivity to acrylic acid has also been observed by the addition of water vapor in the feed of propane and oxygen in the oxidation of propane.

关键词： oxidation of propane surface acidity alkaline earth doped Mo-V-Sb-Ox catalysts acrylic acid acetic acid

Influence of alkali metal doping on surface properties and catalytic activity/selectivity of CaO catalysts in oxidative coupling of methane

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Journal of Natural Gas Chemistry 2008年第4期17卷 313-320页

作者： V.H.Rane S.T.Chaudhari V.R.Choudhary chemical engineering and Process Development division National Chemical Laboratory

Surface properties （viz. surface area, basicity/base strength distribution, and crystal phases） of alkali metal doped CaO （alkali metal/Ca= 0.1 and 0.4） catalysts and their catalytic activity/selectivity in oxidative coupling of methane （OCM） to higher hydrocarbons at different reaction conditions （viz. temperature, 700 and 750 ℃; CH4/O2 ratio, 4.0 and 8.0 and space velocity, 5140-20550 cm^3 ·g^-1·h^-1） have been investigated. The influence of catalyst calcination temperature on the activity/selectivity has also been investigated. The surface properties （viz. surface area, basicity/base strength distribution） and catalytic activity/selectivity of the alkali metal doped CaO catalysts are strongly influenced by the alkali metal promoter and its concentration in the alkali metal doped CaO catalysts. An addition of alkali metal promoter to CaO results in a large decrease in the surface area but a large increase in the surface basicity （strong basic sites） and the C2＋ selectivity and yield of the catalysts in the OCM process. The activity and selectivity are strongly influenced by the catalyst calcination temperature. No direct relationship between surface basicity and catalytic activity/selectivity has been observed. Among the alkali metal doped CaO catalysts, Na-CaO （Na/Ca = 0.1, before calcination） catalyst （calcined at 750 ℃）, showed best performance （C2＋ selectivity of 68.8% with 24.7% methane conversion）, whereas the poorest performance was shown by the Rb-CaO catalyst in the OCM process.

关键词： oxidative coupling of methane alkali metal doped CaO catalysts basicity/base strength distribution catalytic activity/selectivity

Extra low friction coefficient caused by the formation of a solid-like layer:A new lubrication mechanism found through molecular simulation of the lubrication of MoS_2 nanoslits

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Chinese Journal of chemical engineering 2018年第12期26卷 2412-2419页

作者： Jiahui Li Yudan Zhu Yumeng Zhang Qingwei Gao Wei Zhu Xiaohua Lu Yijun Shi College of chemical engineering State Key Laboratory of Materials-oriented Chemical Engineering Nanjing Tech University Energy engineering Division of Energy Science Lule? University of Technology division of Machine Elements Lule? University of Technology

Monolayer molybdenum disulfide(MoS2) is a novel two-dimensional material that exhibits potential application in lubrication technology. In this work, molecular dynamics was used to investigate the lubrication behaviour of different polar fluid molecules(i.e., water, methanol and decane) confined in monolayer Mo S2 nanoslits. The pore width effect(i.e., 1.2, 1.6 and 2.0 nm) was also evaluated. Results revealed that decane molecules exhibited good lubricating performance compared to the other two kinds of molecules. The friction coefficient followed the order of decane b methanol b water, and decreased evidently as the slit width increased, except for decane. Analysis of the spatial distribution and mobility of different confined fluid molecules showed that a solid-like layer was formed near the slit wall. This phenomenon led to the extra low friction coefficient of confined decane molecules.

关键词： Molecular dynamics simulation Microstructure Molybdenum disulfide Residence time distribution

Preparation and Performance of Ternary Early Strength Agent and Quercetin Composite Cement Sealing Material

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Journal of Wuhan University of Technology(Materials science) 2025年第1期 130-140页

作者：刘健 CHEN Meiting 吉小利 XU Chao WANG Chunmei Department of Safety science and engineering Anhui University of Science and Technology Key Laboratory of Mine Safety and High Efficient Mining Jointly Built by Province and Education Ministry Anhui University of Science and Technology Department of chemical engineering and Explosives Anhui University of Science and Technology

A ternary early-strengthening agent consisting of calcium formate + triethanolamine + lithium sulfate was compounded with quercetin to shorten the setting time of cementitious materials while ensuring their early *** optimum ratio of the three early-strengthening agents was determined as 0.5% calcium formate + 0.04% triethanolamine + 0.4% lithium sulfate by response surface *** effects of the ternary early-strengthening agent composed of calcium formate + triethanolamine(TEA)+ lithium sulfate on cementitious pore sealing materials under the synergistic effect of quercetin were studied by means of the performance tests of compressive strength,fluidity,and setting time,and the microstructural characterizations of X-ray powder diffractometer(XRD),thermogravimetry (TG-DSC) and scanning electron microscopy (SEM).The study shows that the synergistic effect of ternary early-strengthening agent and quercetin forms a multi-performance composite admixture for cementitious *** best performance was obtained with the compounding scheme of 0.5% calcium formate + 0.04% triethanolamine + 0.4% lithium sulfate ternary early-strengthening agent and 0.05% *** compressive strength of 1,3,7,and 28 d are 94.8%,39.8%,42%,and 28% higher than those of the blank group,*** initial time and final setting time are 41 and 57 minutes,*** to the microscopic analysis,the network and fibrous C-S-H gels generated by ternary early-strengthening agents are attached to the surface promoted by quercetin,which forms skeleton support while thickening and solidifying the cement slurry,which enhances the early compressive strength of the cement-based materials.

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CO_2/N_2 separation using supported ionic liquid membranes with green and cost-effective [Choline][Pro]/PEG200 mixtures

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Chinese Journal of chemical engineering 2016年第11期24卷 1513-1521页

作者： Tengteng Fan Wenlong Xie Xiaoyan Ji Chang Liu Xin Feng Xiaohua Lu College of Chemistry and chemical engineering State Key Laboratory of Materials-Oriented Chemical EngineeringNanjing Tech University division of Energy science/Energy engineering Lule? University of Technology

The high price and toxicity of ionic liquids(ILs) have limited the design and application of supported ionic liquid membranes(SILMs) for CO_2 separation in both academic and industrial fields. In this work, [Choline][Pro]/polyethylene glycol 200(PEG200) mixtures were selected to prepare novel SILMs because of their green and costeffective characterization, and the CO_2/N_2 separation with the prepared SILMs was investigated experimentally at temperatures from 308.15 to 343.15 K. The temperature effect on the permeability, solubility and diffusivity of CO_2 was modeled with the Arrhenius equation. A competitive performance of the prepared SILMs was observed with high CO_2 permeability ranged in 343.3–1798.6 barrer and high CO_2/N_2 selectivity from 7.9 to *** was also found that the CO_2 permeability increased 3 times by decreasing the viscosity of liquids from 370 to38 m Pa·s. In addition, the inherent mechanism behind the significant permeability enhancement was revealed based on the diffusion-reaction theory, i.e. with the addition of PEG200, the overall resistance was substantially decreased and the SILMs process was switched from diffusion-control to reaction-control.

关键词： CO2/N2separation Supported ionic liquid membranes (SILMs) [Choline][Pro]/PEG200 Diffusion-reaction theory