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学者姓名：郑寿添
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Abstract ：
Ln-containing polyoxoniobates (PONbs) have appealing applications in luminescence, information encryption and magnetic fields, but the synthesis of PONbs containing high-nuclearity Ln-O clusters is challenging due to the easy hydrolysis of Ln3 + ions in alkaline environments. In this paper, we are able to integrate CO3 2- and high-nuclearity Ln-O clusters into PONb to construct an inorganic giant Eu19 -embedded PONb H49 K16 Na13 (H2 O)63 [Eu21 O2 (OH)7 (H2 O)5 (Nb7 O22 )10 (Nb2 O6 )2 (CO3 )18 ] 91H2 O ( 1 ), which contains the highest nuclearity Eu-O clusters and the largest number of Eu3 + ions among PONbs. In addition, the film that was prepared by mixing 1 with gelatin and glycerol, exhibits reversible luminescence switching behavior under acid/alkali stimulation and has been used to create a fluorescence-encoded information approach. This work paves a feasible strategy for the construction of high-nuclearity Ln-O cluster-containing PONbs and the expansion of the application of Ln-containing PONbs in information encryption. (c) 2024 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
Keyword ：
Acid/alkali stimulation Acid/alkali stimulation Information encryption Information encryption Lanthanide Lanthanide Luminescence Luminescence Polyoxoniobate Polyoxoniobate
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| GB/T 7714 | Xia, Wen-Jun , Wang, Yong-Jiang , Cao, Yun-Fei et al. A luminescent folded S-shaped high-nuclearity Eu19 -oxo-cluster emb e dde d polyoxoniobate for information encryption [J]. | CHINESE CHEMICAL LETTERS , 2025 , 36 (2) . |
| MLA | Xia, Wen-Jun et al. "A luminescent folded S-shaped high-nuclearity Eu19 -oxo-cluster emb e dde d polyoxoniobate for information encryption" . | CHINESE CHEMICAL LETTERS 36 . 2 (2025) . |
| APA | Xia, Wen-Jun , Wang, Yong-Jiang , Cao, Yun-Fei , Sun, Cai , Li, Xin-Xiong , Sun, Yan-Qiong et al. A luminescent folded S-shaped high-nuclearity Eu19 -oxo-cluster emb e dde d polyoxoniobate for information encryption . | CHINESE CHEMICAL LETTERS , 2025 , 36 (2) . |
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In the past, the synthesis of polyoxometalate (POM)-templated silver nanoclusters typically relied on the use of organic salts of POMs as starting templates, thereby limiting the solvent selectivity in the synthesis. The utilization of pure-inorganic POMs as starting templates in developing novel POM-templated silver nanoclusters has been neglected. Herein, we have used pure-inorganic polyoxoniobates as a starting template to synthesize a new silver nanocluster H4[Nb6O19@Ag40(iPrS)28S4] (Ag40) (iPrS = isopropylthiolate). Single-crystal X-ray diffraction analysis showed that the silver nanocluster exhibits a remarkable core-shell structure featuring a Lindqvist-type [Nb6O19]8- polyanion as a template, surrounded by 40-nucleated silver ions as the metal shell and capped by iPrS- ligands. Interestingly, the silver nanocluster exhibits significant fluorescence properties at low temperatures, demonstrating temperature-dependent fluorescence, making it a potential candidate for temperature sensing. This work provides a new strategy for new POM-templated silver nanoclusters by using pure-inorganic POMs as starting templates. It also offers new insights into the anionic template method for synthesizing silver nanoclusters.
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| GB/T 7714 | Zeng, Li , Lin, Ya-Ting , Hong, Li-Hao et al. A new silver-thiolate nanocluster synthesized utilizing pure-inorganic polyoxoniobate as a starting template and its variable-temperature fluorescence properties [J]. | CRYSTENGCOMM , 2025 , 27 (18) : 2883-2887 . |
| MLA | Zeng, Li et al. "A new silver-thiolate nanocluster synthesized utilizing pure-inorganic polyoxoniobate as a starting template and its variable-temperature fluorescence properties" . | CRYSTENGCOMM 27 . 18 (2025) : 2883-2887 . |
| APA | Zeng, Li , Lin, Ya-Ting , Hong, Li-Hao , Sun, Yan-Qiong , Xie, Jianping , Zheng, Shou-Tian et al. A new silver-thiolate nanocluster synthesized utilizing pure-inorganic polyoxoniobate as a starting template and its variable-temperature fluorescence properties . | CRYSTENGCOMM , 2025 , 27 (18) , 2883-2887 . |
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A series of novel cage-like transition-metal (TM) incorporated heteropolyoxoniobates {TM4Nb64O200} (1-TM, TM = Ni, Cu, Mn, Cd) were hydrothermally synthesized and isolated as salts of mixed K+ and [CN3H6]+. As a result of transition metal ions incorporation, the charge distribution, redox potential, and active sites of the formed polyoxoniobates (PONbs) are variants, leading to differences in their electrocatalytic hydrogen evolution reaction (HER). Among these compounds, 1-Ni showed the best HER activity with an overpotential of 560 mV at 10 mA cm-2 and a minimum Tafel slope of 405.8 mV dec-1.
Keyword ：
Cage-like Cage-like Hydrogen evolution reaction Hydrogen evolution reaction Polyoxometalate Polyoxometalate Transition metal substitution Transition metal substitution
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| GB/T 7714 | Wu, Lan , Hu, Fen , Sun, Rong-Zhi et al. Development of cage-like transition-metal incorporated polyoxoniobates for hydrogen evolution reaction electrocatalysts [J]. | JOURNAL OF SOLID STATE CHEMISTRY , 2025 , 345 . |
| MLA | Wu, Lan et al. "Development of cage-like transition-metal incorporated polyoxoniobates for hydrogen evolution reaction electrocatalysts" . | JOURNAL OF SOLID STATE CHEMISTRY 345 (2025) . |
| APA | Wu, Lan , Hu, Fen , Sun, Rong-Zhi , Xia, Wen-Jun , Zeng, Qing-Xin , Cai, Ping-Wei et al. Development of cage-like transition-metal incorporated polyoxoniobates for hydrogen evolution reaction electrocatalysts . | JOURNAL OF SOLID STATE CHEMISTRY , 2025 , 345 . |
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Herein, cobalt ammine complexes are combined with alkali-resistant polyoxoniobates (PONbs) at the molecular level to obtain two new organic-inorganic hybrid Co-containing PONbs with the same polyanions but different Co contents. The Co-containing PONb with higher Co content exhibits superior hydrogen evolution reaction (HER) activity under highly alkaline conditions, which is better than the results for the similar Cu-containing PONb, highlighting the critical role of cobalt in improving HER performance. This study provides a new insight into the relationship between the structural properties of metal complexes during electrocatalysis.
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| GB/T 7714 | Chen, Chun-Xia , Duan, Shui-Lin , Zhang, Xiao-Yue et al. Organic-inorganic hybrid Co-containing polyoxoniobates as hydrogen evolution catalysts in alkaline media [J]. | DALTON TRANSACTIONS , 2025 , 54 (9) : 3591-3596 . |
| MLA | Chen, Chun-Xia et al. "Organic-inorganic hybrid Co-containing polyoxoniobates as hydrogen evolution catalysts in alkaline media" . | DALTON TRANSACTIONS 54 . 9 (2025) : 3591-3596 . |
| APA | Chen, Chun-Xia , Duan, Shui-Lin , Zhang, Xiao-Yue , Sun, Rong-Zhi , Cai, Ping-Wei , Sun, Cai et al. Organic-inorganic hybrid Co-containing polyoxoniobates as hydrogen evolution catalysts in alkaline media . | DALTON TRANSACTIONS , 2025 , 54 (9) , 3591-3596 . |
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Three novel inorganic-organic hybrid polyoxoniobates (PONbs), H27K2Na6(H2O)17[K(H2O)(Nb6O19)2(Nb6O20) (RA)2]center dot 13H2O (1, H5RA = C7H11NO7P2, risedronic acid), H21(CN3H6)12[K3(H2O)(Nb6O19)2(Nb6O20)(ZA)2]center dot 5H2O (2, H5ZA = C5H10N2O7P2, zoledronic acid, CN3H6 = guanidine) and H24(CN3H6)7K2(H2O)4[K3(H2O)2(Nb6O19)2(Nb6O20)(EA)2]center dot 8H2O (3, H5EA = C2H8O7P2, etidronic acid, CN3H6 = guanidine) were successfully synthesized. The polyoxoanion clusters are in a small boat shape and consist of {(Nb6O19)2(Nb6O20)} unit and two deprotonated RA5-, ZA5-, and EA5- ligands, respectively. Furthermore, PONb 1 can be used as an effective heterogeneous catalyst for the Knoevenagel condensation reaction with high yields and good substrate compatibility under optimal conditions. In addition, PONb 1 also has good catalytic activity in gram-scale reactions.
Keyword ：
Knoevenagel condensation reaction Knoevenagel condensation reaction Organophosphonate Organophosphonate Polyoxoniobate Polyoxoniobate
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| GB/T 7714 | Zhang, Xue-Yu , Li, Yan-Ru , Hong, Li-Hao et al. Bisphosphonate-modified boat-shaped polyoxoniobates for efficient catalysis of knoevenagel condensation [J]. | JOURNAL OF SOLID STATE CHEMISTRY , 2025 , 347 . |
| MLA | Zhang, Xue-Yu et al. "Bisphosphonate-modified boat-shaped polyoxoniobates for efficient catalysis of knoevenagel condensation" . | JOURNAL OF SOLID STATE CHEMISTRY 347 (2025) . |
| APA | Zhang, Xue-Yu , Li, Yan-Ru , Hong, Li-Hao , Wu, Ping-Xin , Cong, Yu-Chen , Mi, Ying-Hao et al. Bisphosphonate-modified boat-shaped polyoxoniobates for efficient catalysis of knoevenagel condensation . | JOURNAL OF SOLID STATE CHEMISTRY , 2025 , 347 . |
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Here, a case of bilayer heterojunction Pd-containing polyoxotungstate (POW), connecting a Te3Pd3 ring and an Anderson-like TeW6 cluster, has been synthesized. The Anderson-like cluster is the first example in POW. The coordination of Pd in the ring with the S atom on the sulfo group breaks the traditional coordination configuration of Pd and O in polyoxometalates (POMs), enriching the structural types of Pd-containing POMs. In addition, the hybrid bilayer heterojunction structure at the molecular level not only provides high thermal stability but also results in spatial arrangement anisotropy, leading to up to five times the anisotropic proton conductivity. © 2024 American Chemical Society.
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| GB/T 7714 | Jia, L. , Liu, Y.-X. , Li, X.-X. et al. A Palladium-Containing Polyoxotungstate with Anisotropic Proton Conductivity [J]. | Inorganic Chemistry , 2024 , 63 (31) : 14308-14312 . |
| MLA | Jia, L. et al. "A Palladium-Containing Polyoxotungstate with Anisotropic Proton Conductivity" . | Inorganic Chemistry 63 . 31 (2024) : 14308-14312 . |
| APA | Jia, L. , Liu, Y.-X. , Li, X.-X. , Sun, C. , Zheng, S.-T. . A Palladium-Containing Polyoxotungstate with Anisotropic Proton Conductivity . | Inorganic Chemistry , 2024 , 63 (31) , 14308-14312 . |
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Nature seems to favor the formation of closed anion-templated silver clusters. How precisely to create non-closed sliver clusters remains an interesting challenge. In this work, we propose that the use of transition-metal-coordination-cluster substituted polyoxometalates (TMCC-substituted POMs) as templates is an effective synthetic strategy for creating the non-closed silver clusters, as demonstrated by the obtainment of four types of rare non-closed silver cluster species of Ag38-TM (TM = Co, Ni or Zn), Ag37-Zn, {Ag37-Zn}∞ and Ag36-TM (TM = Co, Ni). The idea of the strategy is to employ the TMCC-substituted POMs containing cluster modules with different bond interactions with Ag+ ions as templates to guide the formation of the non-closed silver clusters. For example, TMCC-substituted POM clusters are used as templates in this work, which contain POM modules that can coordinate with the Ag+ ions and TMCC moieties that are difficult to coordinate with the Ag+ ions, leading to the Ag+ ions being unable to form closed clusters around TMCC-substituted POM templates. The work demonstrates a promising approach to developing intriguing and unexplored non-closed silver clusters. © 2024 The Royal Society of Chemistry.
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| GB/T 7714 | Ge, R. , Cai, P.-W. , Sun, C. et al. Development of non-closed silver clusters by transition-metal-coordination-cluster substituted polyoxometalate templates [J]. | Chemical Science , 2024 , 15 (31) : 12543-12549 . |
| MLA | Ge, R. et al. "Development of non-closed silver clusters by transition-metal-coordination-cluster substituted polyoxometalate templates" . | Chemical Science 15 . 31 (2024) : 12543-12549 . |
| APA | Ge, R. , Cai, P.-W. , Sun, C. , Sun, Y.-Q. , Li, X.-X. , Zheng, S.-T. . Development of non-closed silver clusters by transition-metal-coordination-cluster substituted polyoxometalate templates . | Chemical Science , 2024 , 15 (31) , 12543-12549 . |
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Polyoxometalate (POM)-based materials are ideal candidates for implementing molecular memories, and rational POM molecule design is key to higher resistive switching (RS) performance. In this work, in order to obtain a deep structure-property correlation of POM-based memristors, three Anderson-based hybrids, i.e. two-component hybrids (MV)3(MnMo6O18L2)2·4DMF (1) and (MV)2[Cu(DMF)2](MnMo6O18L1)2·6DMF (2), and the three-component one (MV)2(Cu2I3)(MnMo6O18L2)·4CH3CN (3) (L = 2-(hydroxymethyl)-2-(pyridine-4-yl)-1,3-propanediol) have been structurally determined. These hybrids together with the precursors (methyl viologen (MV2+), CuI, and (MnMo6O18L2)) were further fabricated as memristors with the structure of ITO/active layer/Ag. Interestingly, three precursors are RS silent or have bad RS performance, but the incorporation of MV2+ in 1 and 2 can trigger the RS performances, and the further decoration of iodocuprate in 3 can render enhanced RS behavior (ON/OFF ratio: 2.32 × 102) with high thermal-tolerance temperature (240 °C) and extremely long-term stability. The RS mechanism could be assigned to the valence change (VC) induced by oxygen vacancy migrations. The presence of air-stable (MnMo6O18L2)3−-MV2+ donor-acceptor couples can stabilize the oxygen vacancies, which not only trigger the RS behaviors in ITO/1/Ag and ITO/2/Ag, but also result in extremely long-term stability in ITO/3/Ag. Besides, the oxygen vacancies can also be stabilized by Cu2I3 with intense cuprophilic interactions, which corresponds to enhanced RS properties in ITO/3/Ag. This mechanism could be validated by the following structural characters in 3: the stronger POM-MV2+ interactions, the better planarity of MV2+, the very short Cu⋯Cu distances and the ABAB-type packing fashion. The structure-property correlation in this work can provide a new strategy for the development of highly efficient and reliable memristors. © 2024 The Royal Society of Chemistry.
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| GB/T 7714 | Chen, H.-B. , He, M.-Y. , Li, T. et al. Exploring the role of viologen and iodocuprate in the enhanced resistive switching performance of Anderson polyoxometalate-based three-component hybrids [J]. | Journal of Materials Chemistry C , 2024 , 12 (34) : 13555-13561 . |
| MLA | Chen, H.-B. et al. "Exploring the role of viologen and iodocuprate in the enhanced resistive switching performance of Anderson polyoxometalate-based three-component hybrids" . | Journal of Materials Chemistry C 12 . 34 (2024) : 13555-13561 . |
| APA | Chen, H.-B. , He, M.-Y. , Li, T. , Deng, C.-C. , Xiao, H.-P. , Qi, M.-Q. et al. Exploring the role of viologen and iodocuprate in the enhanced resistive switching performance of Anderson polyoxometalate-based three-component hybrids . | Journal of Materials Chemistry C , 2024 , 12 (34) , 13555-13561 . |
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An all-inorganic three-dimensional (3D) polyoxoniobate (PONb) framework, Na6K4[(Nb6O19)CrIII(H2O)2]2·38H2O (1) has been synthesized via the hydrothermal method. The fundamental building unit of [(Nb6O19)CrIII(H2O)2]210− is connected by K+ ions, forming a 3D framework structure with channels along the b-axis. Compound 1 exhibits good thermal stability, and selectively absorbs Co2+ ions while excluding Ni2+ ions from acetonitrile solutions, PXRD analysis confirms that its framework remains intact after adsorption, indicating its potential as an effective ion-exchange material. © 2024 Elsevier Inc.
Keyword ：
Ion exchange Ion exchange Polyoxometalate Polyoxometalate Polyoxoniobate Polyoxoniobate
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| GB/T 7714 | Lian, X.-K. , Mi, Y.-H. , Wu, P.-X. et al. A chromium-incorporated all-inorganic polyoxoniobate framework material: Good chemical stability and selective ion exchange capability [J]. | Journal of Solid State Chemistry , 2024 , 338 . |
| MLA | Lian, X.-K. et al. "A chromium-incorporated all-inorganic polyoxoniobate framework material: Good chemical stability and selective ion exchange capability" . | Journal of Solid State Chemistry 338 (2024) . |
| APA | Lian, X.-K. , Mi, Y.-H. , Wu, P.-X. , Zeng, Q.-X. , Zheng, S.-T. , Li, X.-X. . A chromium-incorporated all-inorganic polyoxoniobate framework material: Good chemical stability and selective ion exchange capability . | Journal of Solid State Chemistry , 2024 , 338 . |
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A rare all-inorganic high-nuclearity mixed-valent {Mn11} cluster embedded polyoxoniobate, K25H43{(Te4Nb9O33)3(Nb6O19)5(TeVINb5O14)[(TeIVO3)2(MnII7MnIII4O19)]}·97H2O (1), has been synthesized by a one-pot reaction. Compound 1 contains the largest manganese cluster {Mn11} core among polyoxoniobates reported to date. {Mn11} consists of three quasi-cubane {Mn3O4} units and is simultaneously encapsulated by lacunary α-Keggin {Te4Nb9O36} and Lindqvist {Nb6O19} units. Compound 1 exhibits significant magnetic anisotropy and excellent water solubility and stability. The findings suggest a new, all-inorganic polynulear Mn-based structural paradigm for aqueous solution chemistry and magnetic materials. © 2024 The Royal Society of Chemistry.
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| GB/T 7714 | Wu, P.-X. , Chen, C.-X. , Sun, Y.-Q. et al. A water-soluble mixed-valent {Mn11} cluster embedded heteropolyoxoniobate with magnetic properties [J]. | Chemical Communications , 2024 , 60 (67) : 8888-8891 . |
| MLA | Wu, P.-X. et al. "A water-soluble mixed-valent {Mn11} cluster embedded heteropolyoxoniobate with magnetic properties" . | Chemical Communications 60 . 67 (2024) : 8888-8891 . |
| APA | Wu, P.-X. , Chen, C.-X. , Sun, Y.-Q. , Zheng, S.-T. . A water-soluble mixed-valent {Mn11} cluster embedded heteropolyoxoniobate with magnetic properties . | Chemical Communications , 2024 , 60 (67) , 8888-8891 . |
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