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Recent progress on photoactive nonprecious transition-metal complexes

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Science China Chemistry 2025年第1期68卷 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.

关键词： photoactive metal complexes earth-abundant metals nonprecious metal complexes luminescence photochemistry

Synthesis of chiral phosphine derivatives through a copper（I）-catalyzed desymmetric SNAr reaction

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Science China Chemistry 2025年

作者： shuai Zhang Pei-Zhi liu Yan-Bo Li Qi Zhang Jun-Zhao Xiao Yi-Fan Wang Tian-Yu Wei Jia-Wei Jiang Ye Wang Qian Peng Liang Yin Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences State Key Laboratory of Elemento-Organic Chemistry and Tianjin Key Laboratory of Biosensing and Molecular Recognition College of Chemistry Frontiers Science Center for New Organic Matter Nankai University Haihe Laboratory of Sustainable Chemical Transformations

Axially chiral phosphines are a class of extremely important ligands in asymmetric catalysis. Herein, an unprecedented copper（I）-catalyzed asymmetric SNAr reaction with HP（S）R2is uncovered, which delivers a series of axially chiral phosphine derivatives in high yields with excellent enantioselectivity. Furthermore, the diastereoselective reaction with the kinetic resolution of racemic HP（S）ArR proceeds smoothly, providing the products with moderate diastereoselectivity and excellent enantioselectivity. Control experiments indicate that HP（S）Ph2is much more active than HPPh2and HP（O）Ph2as the pronucleophile in the present reaction. It is found that the SNAr reaction （the first SNAr） proceeds in a desymmetric manner, providing the desired chiral products while a continued SNAr reaction （the second SNAr） slightly occurs in a kinetic resolution manner in the present catalytic system, which enhances the ee of the desired chiral products. DFTcalculations support a concerted reaction pathway rather than a step-wise mechanism. Finally, axially chiral olefin-phosphines produced by the present method work as suitable ligands in Pdcatalyzed asymmetric allylic substitution with C-, N-, and O-nucleophiles and Rh-catalyzed asymmetric addition of arylboronic acid to benzil.

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Economic effect of China's carbon neutrality target under shared socioeconomic pathways

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Science China Earth Sciences 2025年第1期68卷 142-157页

作者： Zemiao liu Xianjin HUANG Xinxian QI School of Geography and Ocean Science Nanjing University Key Laboratory of Carbon Neutrality and Territory Optimization Ministry of Natural Resources Frontiers Science Center for Critical Earth Material Cycling Nanjing University

Economic feasibility is crucial for achieving the carbon neutrality target. However, current integrated assessments often underestimate the economic impacts of mitigation policies due to the lack of consideration of their economic benefits. This study integrates a warming-labour productivity model with a typical integrated assessment model using shared socioeconomic pathways. It simulates China's economic development and carbon emission levels under both baseline and carbon-neutral policy scenarios, evaluating the economic costs and benefits of emission reduction policies aimed at achieving carbon neutrality. These findings reveal the following:(1) The economic costs of emission reduction policies are projected to peak between 2050 and 2060, ranging from 0.41% to 9.37% of total GDP in the baseline scenario, primarily due to increased energy prices and R&D investments. These costs are expected to decline rapidly after 2070.(2) China's carbon-neutral policies will mitigate global warming, with the economic benefits of mitigation projected to reach 5.65% to 17.24% of China's total GDP by 2100.(3) Lowcarbon scenarios SSP1 and SSP4 could significantly reduce initial economic costs and advance the onset of net economic gains to 2060. This integrated assessment confirms that China's carbon neutrality target offers substantial net economic benefits in the long term. To minimize initial economic costs, efforts should focus on enhancing consumption-side transitions, upgrading lowcarbon technologies, and adopting new energy sources.

关键词： Climate change China Carbon neutrality Economic effects Policy

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种植模式对农田水-沙-氮磷流失特征的影响研究

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吉林水利 2025年第1期 40-45页

作者：刘帅水发规划设计有限公司山西分公司山西太原030027

在作物生产的过程中,由降雨、灌溉等因素造成的农田土壤侵蚀及氮磷流失会导致土地生产力退化,威胁粮食生产,因此需要分析农田土壤侵蚀及氮磷流失的影响因素。不同种植模式对水土保持有着不同的影响,本文围绕旱作、水作及水旱轮作3种种... 详细信息

在作物生产的过程中,由降雨、灌溉等因素造成的农田土壤侵蚀及氮磷流失会导致土地生产力退化,威胁粮食生产,因此需要分析农田土壤侵蚀及氮磷流失的影响因素。不同种植模式对水土保持有着不同的影响,本文围绕旱作、水作及水旱轮作3种种植模式,对自然降雨条件下的产流产沙及径流氮磷流失规律进行研究,明确流失特征,其结果可为农田水土保持和粮食生产安全提供参考。

关键词：土壤侵蚀种植模式氮磷流失

Oxidation Resistance of Form-stable Hightemperature Phase Change Thermal Energy Storage Materials Doped by Impregnated Graphite

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Journal of Wuhan University of Technology(Materials Science) 2025年第1期40卷 1-12页

作者： LI Baorang DAI Jianhuan ZHANG Wei liu Xiangchen YANG liu School of Energy Power and Mechanical Engineering North China Electric Power UniversityBeijing 102206China School of Ener-gy and Environment Southeast UniversityNanjing 210096China

We adopted the solution impregnation route with aluminum dihydrogen phosphate solution as liquid medium for effective surface modification on graphite *** mass ratio of graphite to Al(H_(2)PO_(4))_(3) changed from 0.5:1 to 4:1,and the impregnation time changed from 1 to 7 *** typical composite phase change thermal storage materials doped with the as-treated graphite were fabricated using form-stable *** investigate the oxidation and anti-oxidation behavior of the impregnated graphite at high temperatures,the samples were put into a muffle furnace for a cyclic heat *** on SEM,EDS,DSC techniques,analyses on the impregnated technique suggested an optimized processing conditions of a 3 h impregnation time with the ratio of graphite:Al(H_(2)PO_(4))_(3) as 1:3 for graphite impregnation *** investigations on high-temperature phase change heat storage materials doped by the treated graphite suggested excellent oxidation resistance and thermal cycling performance.

关键词： phase change materials graphite impregnation method oxidation,sintering thermal analysis

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Engineering nanoparticle structure at synergistic Ru-Na interface for integrated CO2 capture and hydrogenation

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Journal of Energy Chemistry 2025年第1期100卷 779-791页

作者： Hanzi liu Ling Cen Xinlin Xie Lei liu Zhao Sun Zhiqiang Sun Hunan Engineering Research Center of Clean and Low-Carbon Energy Technology School of Energy Science and Engineering Central South University

The development of dual functional material for cyclic CO2capture and hydrogenation is of great significance for converting diluted CO2into valuable fuels,but suffers from kinetic limitation and deactivation of adsorbent and ***,we engineered a series of RuNa/γ-Al2O3materials,varying the size of ruthenium from single atoms to clusters/*** coordination environment and structure sensitivity of ruthenium were quantitatively investigated at atomic *** findings reveal that the reduced Ru nanoparticles,approximately 7.1 nm in diameter with a Ru-Ru coordination number of 5.9,exhibit high methane formation activity and selectivity at 340°*** Ru-Na interfacial sites facilitate CO2migration through a deoxygenation pathway,involving carbonate dissociation,carbonyl formation,and ***-situ experiments and theoretical calculations show that stable carbonyl intermediates on metallic Ru nanoparticles facilitate heterolytic C–O scission and C–H bonding,significantly lowering the energy barrier for activating stored CO2.

关键词： Carbon capture and utilization

电子烟工作电压对气溶胶中关键成分释放量的影响

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烟草科技 2017年第9期50卷 42-48页

作者：张霞朱东来李寿波吴俊杨帅洪鎏李廷华巩效伟孙志勇韩熠云南中烟工业有限责任公司技术中心昆明市五华区红锦路367号650231

为准确测定电子烟气溶胶中关键成分(1,2-丙二醇、丙三醇和烟碱)的释放量,了解工作电压对其释放量的影响,通过考察内标、萃取剂体积以及萃取时间等因素,建立了检测电子烟气溶胶中1,2-丙二醇、丙三醇和烟碱释放量的气相色谱方法,并在不同... 详细信息

为准确测定电子烟气溶胶中关键成分(1,2-丙二醇、丙三醇和烟碱)的释放量,了解工作电压对其释放量的影响,通过考察内标、萃取剂体积以及萃取时间等因素,建立了检测电子烟气溶胶中1,2-丙二醇、丙三醇和烟碱释放量的气相色谱方法,并在不同工作电压下对3种烟液(烟油)进行了测定。结果表明:(1)方法灵敏度高、重复性好、回收率高,适用于电子烟气溶胶中1,2-丙二醇、丙三醇和烟碱的定量分析。(2)在3.7~6.9 V范围内,随着工作电压的升高,气溶胶中的TPM、1,2-丙二醇、丙三醇和烟碱的释放量均增加,其中TPM释放量与工作电压线性相关(R2≥0.980 6)。(3)烟油中烟碱浓度与气溶胶中烟碱释放量正相关;气溶胶中烟碱与1,2-丙二醇之间的相关性最强(R^2≥0.991 8),表明1,2-丙二醇对烟碱递送起关键作用。(4)方差分析表明工作电压和烟油中烟碱浓度均对气溶胶中烟碱释放量有显著影响,偏η~2值比较表明烟油中烟碱浓度的影响程度略大于工作电压。

关键词：电子烟工作电压气溶胶 1,2-丙二醇丙三醇烟碱

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Distributed Observer for Full-Measured Nonlinear Systems Based on Knowledge of FMCF

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IEEE/CAA Journal of Automatica Sinica 2025年第1期 69-85页

作者： Haotian Xu shuai liu Yueyang Li Ke Li the School of Control Science and Engineering Shandong University and also with Key Laboratory of Machine Intelligence and System Control Ministry of Education IEEE the School of Electrical Engineering University of Jinan

Driven by practical applications, the achievement of distributed observers for nonlinear systems has emerged as a crucial advancement in recent years. However, existing theoretical advancements face certain limitations: They either fail to address more complex nonlinear phenomena, rely on hard-to-verify assumptions, or encounter difficulties in solving system ***, this paper aims to address these challenges by investigating distributed observers for nonlinear systems through the full-measured canonical form(FMCF), which is inspired by full-measured system(FMS) theory. To begin with, this study addresses the fact that the FMCF can only be obtained through the observable canonical form(OCF) in existing FMS *** paper demonstrates that a class of nonlinear systems can directly obtain FMCF through state space equations, independent of OCF. Also, a general method for solving FMCF in such systems is provided. Furthermore, based on the FMCF, A distributed observer is developed for nonlinear systems under two scenarios: Lipschitz conditions and open-loop bounded *** paper establishes their asymptotic omniscience and demonstrates that the designed distributed observer in this study has fewer design parameters and is more convenient to construct than existing approaches. Finally, the effectiveness of the proposed methods is validated through simulation results on Van der Pol oscillators and microgrid systems.

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Boosting cationic and anionic redox activity of Li-rich layered oxide cathodes via Li/Ni disordered regulation

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Journal of Energy Chemistry 2025年第1期100卷 533-543页

作者： Zewen liu Zhen Wu Hao Wang Xudong Zhang Yuanzhen Chen Yongning liu Shengwu Guo Shenghua Chen Yanli Nan Yan liu State Key Laboratory for Mechanical Behavior of Materials Xi'an Jiaotong University School of Materials Science and Engineering Xi'an University of Architecture and Technology Hefei Advanced Computing Center Operation Management Corp Ltd Network Information Center Xi'an Jiaotong University

Lithium-rich layered oxides （LLOs） are increasingly recognized as promising cathode materials for nextgeneration high-energy-density lithium-ion batteries （LIBs）.However,they suffer from voltage decay and low initial Coulombic efficiency （ICE） due to severe structural degradation caused by irreversible O ***,we introduce a three-in-one strategy of increasing Ni and Mn content,along with Li/Ni disordering and TM–O covalency regulation to boost cationic and anionic redox activity simultaneously and thus enhance the electrochemical activity of *** target material,Li1.2Ni0.168Mn0.558Co0.074O2（L1）,exhibits an improved ICE of 87.2%and specific capacity of 293.2 mA h g-1and minimal voltage decay of less than 0.53 m V cycle-1over 300 cycles at 1C,compared to Li1.2Ni0.13Mn0.54Co0.13O2（Ls）(274.4 mA h g-1for initial capacity,73.8%for ICE and voltage decay of 0.84 mV/cycle over 300 cycles at 1C).Theoretical calculations reveal that the density of states （DOS） area near the Fermi energy level for L1 is larger than that of Ls,indicating higher anionic and cationic redox reactivity than ***,L1 exhibits increased O-vacancy formation energy due to higher Li/Ni disordering of 4.76%（quantified by X-ray diffraction Rietveld refinement） and enhanced TM–O covalency,making lattice O release more difficult and thus improving electrochemical *** increased Li/Ni disordering also leads to more Ni2+presence in the Li layer,which acts as a pillar during Li+de-embedding,improving structural *** research not only presents a viable approach to designing low-Co LLOs with enhanced capacity and ICE but also contributes significantly to the fundamental understanding of structural regulation in high-performance LIB cathodes.

关键词： Ice