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Science China Chemistry 2025年

作者： Jun-Qiang Chen Qiao-Hong Li Qin-Long Hong Ping Shao Hai-Xia Zhang Jian Zhang State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences

Single-atom catalyst has garnered widespread attention to mimic mature enzymes due to its well-defined atomic structure and coordination environments. However, since the carbon–carbon（C–C） coupling reactions require synergistic catalysis of multiple sites, single-atom catalysts suffer from insufficient active sites and unclear reaction mechanisms. Controlling the reaction intermediates in a precisely targeted pocket through careful metal–organic cage design is therefore crucial. Here, we prepare a tetrahedral [Cu6L4]-type boron–imidazolate cage integrating highly active Cu sites and optimized cavity, which exhibits enzyme like specific catalytic performance in electrochemical CO2reduction reaction（CO2RR） to enhance the selectivity of *** analyses and computational calculations suggest that the single Cu site together with neighboring boron–imidazolate ligands provides suitably synergistic effects that enable the energetically favorable formation of an *COCHO intermediate, a key step determining selectivity. As a result, the [Cu6L4]-type cage of BIC-145 achieves a Faradaic efficiency of 28% for C2H4maintaining an average current density of -3.54 mA cm-2over a 5-hour electrolysis period. This work represents the first example for studying single-metal site catalysts with ultra-low coordination numbers through the rational design of metal–organic cages.

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Breaking the structural symmetry of active sites in zeolite imidazolate framework for enhanced CO2 photoreduction

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Science China Chemistry 2025年

作者： Yupeng Han Yayu Yan Qiaohong Li Xin Wu Fei Wang Jian Zhang State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences University of Chinese Academy of Sciences College of Chemistry Fuzhou University

Adjusting the structure and composition of active sites is a highly effective method for activating linear ***, precise control of interfacial chemistry within molecular-scale environments presents a significant challenge in heterogeneous catalysis. In our study, we present symmetry-broken Mo-O-Co triple-atom active sites within the hybrid zeolite imidazole framework HZIF-CoMo. These sites disrupt the electronic balance and create a weak built-in electric field, thus promoting photocatalytic CO2reduction. The CO yield over HZIF-CoMo is improved to 3.1 mmol g-1h-1, which is over four times higher than the parent cobalt-imidazole framework MAF-6-Co. Both experimental and theoretical studies indicate that electronic modulation through the symmetry-breaking Mo-O-Co moiety acts as an organizing knob to accelerate charge separation and result in more carriers participating in the catalytic reaction. This work provides important insights into optimizing site-related electronic structures for targeted photocatalytic reactions.

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Dual-ligand chiral MOFs exhibiting circularly polarized room temperature phosphorescence for anti-counterfeiting

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Science China Chemistry 2025年

作者： Hongrui Zheng Qingqing Wang Xinchao Wang Fei Wang Shangda Li Jian Zhang State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences Fujian Key Laboratory of Polymer Materials College of Chemistry and Materials Science Fujian Normal University

Advanced chiral optical materials exhibiting circularly polarized room-temperature phosphorescence（CPRTP） possess significant research value. This study facilitates the synthesis of chiral metal-organic frameworks（CMOFs） with good CPRTP performance by implementing a dual-ligand strategy. By self-assembling the luminescent ligand H2BIIM with the chiral ligands L-or D-H2IDPA in the presence of Zn（II） ions, two robust three-dimensional（3D） CMOFs were successfully constructed. These complexes demonstrated intense fluorescence and exhibited prolonged yellow room-temperature phosphorescence（RTP） with a duration of up to 6 s. Notably, they exhibited both circularly polarized fluorescence(glum= ±7.57 × 10-3) and CPRTP(glum=±2.68 × 10-3). These unique properties were effectively utilized in the creation of multi-color anti-counterfeiting patterns,underscoring their promising potential for a wide range of applications.

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Enhancing anion conductivity in a highly alkali-stable eta topologic Cu(Ⅰ) framework via strong electrostatic repulsion

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Science China Chemistry 2025年

作者： Xiaolu Wang Shaohui Guo Chao Suo Fuqiang Zhang Junhao Wang Wenjing Wang Daqiang Yuan Linfeng Liang Xianming Zhang College of Chemistry Taiyuan University of Technology institute of Crystalline Materials Shanxi University School of Chemistry and Materials Science Shanxi Normal University State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences

Metal-organic frameworks （MOFs） based on anion exchange membranes （AEMs） have garnered considerable interest,particularly for their potential to enhance ion conductivity by pre-introducing anions into *** approach is recognized as straightforward and effective for improving ion ***,developing high-performance AEMs is limited by the inherent instability and low resistance of *** study presents a novel 1,3,5-triazineμ3-bridged neutral Cu（I） framework,designated SXU-120 （where SXU represents Shanxi University）.This framework is synthesized using melamine,a widely available industrial product,as the starting material,achieving a high space-time yield exceeding 1.1 kg *** organic ligands and metal ions in SXU-120 are 3-connected,forming a rare eta topology with the point symbol 8～***-120 exhibits exceptional stability,even in a 10 M KOH solution,due to its high density of uncoordinated–NH2and carbonyl ***,the framework’s unique one-dimensional channels,characterized by their electronegativity,interact electrostatically with OH-ions,thereby accelerating OH-ion transfer along these ***,the OH-conductivity of this material reaches an impressive 0.49 S cm-1at 90°C under full humidity for 100 h,representing the highest OH-conductivity reported for MOF-based conductors to *** properties make SXU-120 a promising candidate for efficient AEM materials in next-generation industrial applications.

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Activatable chemiluminescence probe based on four-arm PEGconjugated-pyropheophorbide-a for in vivo autofluorescence-free imaging of peroxynitrite

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Science China Chemistry 2025年

作者： Jianmei Ke Lei Ding Ronggui Lian Cheng Zheng Wenjun Li Aixian Zheng Yupeng Sun Ming Wu Yongyi Zeng Xiaolong Liu Maochun Hong Xiaolong Zhang The United Innovation of Mengchao Hepatobiliary Technology Key Laboratory of Fujian Province Mengchao Hepatobiliary Hospital of Fujian Medical University Ganjiang Innovation Academy Chinese Academy of Sciences School of Rare Earths University of Science and Technology of China College of Chemistry Fuzhou University State Key Laboratory of structure Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences

Peroxynitrite（ONOO-） is a highly reactive nitrogen species that plays pivotal roles in cell signal transduction and physiological or pathological progresses. However, commonly used ONOO-optical imaging probes are still hampered by high background/autofluorescence（fluorescence probe）, short emission wavelength, or poor selectivity in the case of chemiluminescence. Herein,we report a facile method to prepare an activatable chemiluminescence probe（PPA-PEG） with good biocompatibility and functionality for in vivo autofluorescence-free imaging of ONOO-. The PPA-PEG consists of pyropheophorbide-a（PPA）, a typical deep red photosensitizer that acts as both the recognition and signaling element, and 4-arm poly（ethylene glycol）(4-arm PEG), which improves the biosafety and water solubility of probe. These components can self-assemble into nanoparticles（namely PPA-PEG nanoprobe） in aqueous solution. The PPA-PEG nanoprobe showed an ultra-low chemiluminescence signal before interacting with ONOO-, but exhibited good selectivity, high sensitivity and a fast response toward ONOO-. The PPAPEG was successfully applied to image cellular ONOO-changes, as well as the endogenous ONOO-changes in inflammation models and subcutaneous or orthotopic hepatocellular carcinoma（HCC） tumors models in living mice. In vitro and in vivo studies verified the good detection and imaging capabilities of PPA-PEG for peroxynitrite, demonstrating suitable tissue penetration and a high signal-to-background ratio（SBR）. Thus, our nanoprobe can serve as a valuable activatable chemiluminescence imaging tool for studying important peroxynitrite-related chemical and biological applications.

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Tuning the porosity of {Co12IICo8III（μ3-OH）24（X）}11+ supramolecular frameworks by reaction time for D2/H2 separation

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Science China Chemistry 2025年

作者： Zhuozhou Xie Zhu Zhuo Zi-Ang Nan Qing Li Xiufang Li Zi-Xiu Lu Linzhe Lü Jin Liu Luyao Liu Wenjing Wang Wei Wang Daqiang Yuan You-Gui Huang State Key Laboratory of structure Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences University of Chinese Academy of Sciences Xiamen Key Laboratory of Rare Earth Photoelectric Functional Materials Xiamen Institute of Rare Earth Materials Haixi InstitutesChinese Academy of Sciences State Key Laboratory of Physical Chemistry of Solid Surfaces Department of Chemistry College of Chemistry and Chemical EngineeringXiamen University

Systematicly tuning the porosities of porous materials is crucial for targeted gas mixture separation,yet it remains a longstanding *** a common strategy,altering the phenylene ring count in the organic building units has been exploited to adjust pore apertures in metal organic frameworks （MOFs） and covalent organic frameworks （COFs）,resulting in only a stepwise pore size variation of approximately 2.8?.Unlike MOFs and COFs,the porosities for supramolecular assembly frameworks are highly dependent on the packings of the molecular building units in the *** above strategy cannot be applied to supramolecular assembly frameworks and other strategies are required to adjust pore apertures in supramolecular frameworks,especially to achieve porous materials with the optimal pore size for D2/H2separation （～3?）.Here,we successfully modulate the porosity of supramolecular frameworks of[CoII1+12CoIII8L12（μ3-OH）24（X）]1clusters （L=mono-deprotonated 1-iminoisoindole-3-amine,X=ClO?4or Cl?） by controlling the duration of self-assembly *** simply adjusting the reaction time,we obtain three[CoII12CoIII8L12（μ3-OH）24（X）]11+supramolecular frameworks:[CoII12CoIII8（μ3-OH）24（ClO4）L12)]·（Cl）4·（HCO2）7（1）,[CoII12CoIII8L12（μ3-OH）24（Cl）]·（ClOI4）4·（Cl）6·（HCO2）·（H2O）10（2）,and[CoI12CoIII8L12（μ3-OH）24（Cl）]·（Cl）11·（H2O）12（3）.The different stacking patterns of the[CoII12CoIII8L12（μ3-OH）24（X）]11+clusters in these frameworks lead to significantly varied stabilities and *** 1 exhibits permanent porosity with interconnected channels and maintains stability under harsh *** contrast,compound 2 is nearly nonporous,and compound 3 becomes unstable upon *** pores of compound 1 show higher affinity to D2than H2,and the pore aperture diameter of compound 1 （～3.06?） meets the optimal porosity for D2/***,compound 1 demonstrates moderate D2/H2separation at 77 K (retention time:～7 min/g for D2/H2/Ne （10/10/80 vol%） in a flow of 5 mL

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Experimental Study of Nd^(3+):KGd(WO_(4))_(2) Laser Pumped by Laser Diode

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Chinese Physics Letters 1996年第3期13卷 178-181页

作者： ZHAO Ting-jie TU Chao-yang LUO Zun-du fufian institute of research on the structure of matter Chinese Academy of SciencesFuzhou 350002

This paper presents the cw output characteristics of Nd^(3+):KGd(WO_(4))_(2)(KGW)laser crystal with different NcP+concentration grown in our *** laser output at 1.067 μm of KGW crystal(3×3×6 mm)was obtained to be 6... 详细信息

关键词： pumped laser diode

STUDIES ON SYNTHESES OF MoFe_3S_4 CUBANE-LIKE CLUSTER COMPOUNDS

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Science China Chemistry 1989年第4期32卷 392-400页

作者：刘秋田康北笙陈昌能黄梁仁蔡进华庄伯涛卢嘉锡 fufian institute of research on-the structure of matter Academia Sinica Fuzhou

The features of synthetic processes are described on the basis of the studies of the syntheses of MoFe_3S_4 cubane-like cluster compounds either by self-assembly reactions or by the conversion of linear clusters. The redox properties and the structure of ligands as well as the stoichiometry of reactants have obvious effects upon the core oxidation state and the structure of products. It is indicated that the self-assembly reaction may pass through a combination process oflinear cluster intermediates having structural unit (M,M'=Mo) Fe).

关键词： Mo cluster Fe clusters MoFeS clusters heterometallic thiocubane.

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Dramatical enhancement of circular dichroism in chiral hybrid perovskites via carboxylic hydrogen bond engineering

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Science China Chemistry 2025年

作者： Hang Li Xinling Li Peng Wang Tingting Zhu Ruiqing Li Huang Ye Yaru Geng Hongliang Dai Junhua Luo State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences University of Chinese Academy of Sciences Fujian College University of Chinese Academy of Sciences College of Chemistry Fuzhou University College of Chemistry and Materials Key Laboratory of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of EducationJiangxi Normal University

Chiral hybrid perovskites （CHPs） have been regarded as promising candidates for developing chiroptoelectronics ***,circular dichroism （CD）,as one of the most important characteristics to evaluate the chiroptical activity,remains at a comparatively low level in CHPs compared to other chiral materials,which hinders the successful applications of CHPs in stateof-the-art ***,exploring new methods for enhancing CD in CHPs is urgently needed and remains ***,enhanced CD response has been successfully realized via constructing carboxylic hydrogen bonding in chiralachiral mixed cations perovskites （R/S-PPA）2（ABA）PbBr5（2R/2S）(PPA=1-phenylpropylamine,ABA=4-aminobutyric acid).Compared with the prototype （R/S-PPA）PbBr3（1R/1S）,2R/2S provide intimate connections between organic units and inorganic parts via carboxylic hydrogen bonding N–H···O bridge,contributing new chirality transfer paths.A larger inorganic skeletons’helicity in 2R/2S predicts a high degree of chirality ***,2R/2S exhibit significantly enhanced CD response with an anisotropy factor amplified by an order of ***,bright blue circularly polarized luminescence applications are achieved in 2R/*** work systematically investigates the correlation between CD and hydrogen bonding interaction in CHPs,meanwhile providing a new avenue to develop the application potential of chiral materials in chiroptoelectronics.

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Negative PO3-implanted bionic ion transport channels for promoting Li-S battery

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Science China Chemistry 2025年

作者： Wenhuan Huang Shun Wang Xuehan Hou Yanan Zhang Xingxing Zhang Yaoxiao Zhao Xilang Jin Huabin Zhang Fei Wang Jian Zhang Key Laboratory of Chemical Additives for China National Light Industry College of Chemistry and Chemical EngineeringShaanxi University of Science and Technology School of Materials and Chemical Engineering Xi'an Technological University Chemistry Program Physical Science and Engineering Division King Abdullah University of Science and Technology State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences

Lithium-sulfur （Li-S） battery,as a promising next-generation high-energy-density battery,suffers from lithium polysulfides（LPSs） shuttle and Li dendrites *** crystalline framework-based membranes as separator can effectively absorb and restrain LPSs but without precise structural design principal exploration and mechanism ***,bio-inspired 1D oriented lithium-ion transport channels with molecular negatively charged PO3（-1） have been developed in hybrid tetrazole frameworks for promoting the transmission of Li+*** theoretical calculations and in situ spectroscopy demonstrated the higher binding energy and inhibited diffusion of LPSs in *** assembled PP@PO3Janus separator in Li-S coin cell delivered a high initial capacity of 1410.9 mAh g-1at 0.1 C and a low attenuation rate of 0.038%per cycle over 500 cycles at 5 ***,the high capacities of 862,542 and 409 mAh g-1based on high-sulfur-loading cathodes of 2.6,3.8 and 5.0 mg cm-2at0.5 C were achieved,***,the punch battery of PO3@PP separator with S-cathode of 1.2 mg cm-2has been developed for demonstrating its potentials commercial application,which displays impressive capacity of 873.4 mAh g-1with the retention of～78.9%over 50 cycles.

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