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学者姓名：郑寿添
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Abstract ：
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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The novel Sc-containing polyoxoniobate, H16.5K9Na16.5[Sc3(Nb7O22)(Nb14O42)3]115.5H2O, has been successfully synthesized. It exhibits a unique heptameric structure and demonstrates catalytic activity towards the Knoevenagel condensation reaction, along with broad substrate compatibility.
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| GB/T 7714 | Lin, Ya-Ting , Zeng, Li , Li, Yi-Ying et al. A scandium-containing polyoxoniobate heptamer as a catalyst for the Knoevenagel condensation reaction [J]. | DALTON TRANSACTIONS , 2025 , 54 (21) : 8425-8429 . |
| MLA | Lin, Ya-Ting et al. "A scandium-containing polyoxoniobate heptamer as a catalyst for the Knoevenagel condensation reaction" . | DALTON TRANSACTIONS 54 . 21 (2025) : 8425-8429 . |
| APA | Lin, Ya-Ting , Zeng, Li , Li, Yi-Ying , Sun, Yan-Qiong , Li, Xin-Xiong , Zheng, Shou-Tian . A scandium-containing polyoxoniobate heptamer as a catalyst for the Knoevenagel condensation reaction . | DALTON TRANSACTIONS , 2025 , 54 (21) , 8425-8429 . |
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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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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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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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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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Three new group IIIA metal phosphate-oxalate (MPO) compounds, namely [(CH3)2NH2]2[M2(HPO4)2(H2PO4)2(C2O4)] (M = Al (1), Ga (2)) and [(CH3)2NH2]2[In2(HPO4)2(H2PO4)2(C2O4)]center dot H2O (3), have been synthesized. Their crystal structures feature an anionic layer with the sql topology net. In particular, 1 displays a proton conductivity (sigma) of 9.09 x 10-3 S cm-1 at 85 degrees C and under 98% relative humidity, which is the highest among MPOs. This study not only endows the main group metal-based MPO family with new members, but also contributes to further understanding of the structure-directing roles of amines and provides a feasible idea for improving the proton conductivity of MPOs. Three new layered metal phosphate-oxalates [(CH3)2NH2]2[M2(HPO4)2(H2PO4)2(C2O4)]center dot xH2O (M = Al, Ga, In) have been synthesized. [(CH3)2NH2]2[Al2(HPO4)2(H2PO4)2(C2O4)] displays the highest proton conductivity among metal phosphate-oxalates so far.
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| GB/T 7714 | Pan, Tian-Yu , Wen, Wei-Yang , Ma, Wen et al. New group IIIA metal phosphate-oxalates containing dimethylammonium cations with proton conductivity [J]. | DALTON TRANSACTIONS , 2024 , 53 (5) : 2318-2323 . |
| MLA | Pan, Tian-Yu et al. "New group IIIA metal phosphate-oxalates containing dimethylammonium cations with proton conductivity" . | DALTON TRANSACTIONS 53 . 5 (2024) : 2318-2323 . |
| APA | Pan, Tian-Yu , Wen, Wei-Yang , Ma, Wen , Zheng, Shou-Tian , Feng, Mei-Ling , Huang, Xiao-Ying . New group IIIA metal phosphate-oxalates containing dimethylammonium cations with proton conductivity . | DALTON TRANSACTIONS , 2024 , 53 (5) , 2318-2323 . |
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Atomically precise low-nuclearity (n<10) silver nanoclusters (AgNCs) have garnered significant interest due to their size-dependent optical properties and diverse applications. However, their synthesis has remained challenging, primarily due to their inherent instability. The present study introduces a new feasible approach for clustering silver ions utilizing highly negative and redox-inert polyoxoniobates (PONbs) as all-inorganic ligands. This strategy not only enables the creation of novel Ag-PONb composite nanoclusters but also facilitates the synthesis of stable low-nuclearity AgNCs. Using this method, we have successfully synthesized a small octanuclear rhombic [Ag-8](6+) AgNC stabilized by six highly negative [LiNb27O75](14-) polyoxoanions. This marks the first PONb-protected superatomic AgNC, designated as {Ag-8@(LiNb27O75)(6)} (Ag-8@Nb-162), with an aesthetically spherical core-shell structure. The crystalline Ag-8@Nb-162 is stable under ambient conditions, What's more, it is water-soluble and able to maintain its molecular cluster structure intact in water. Further, the stable small [Ag-8](6+) AgNC has interesting temperature- and pH-dependent reversible fluorescence response, based on which a multiple optical encryption mode for anti-counterfeit technology was demonstrated. This work offers a promising avenue for the synthesis of fascinating and stable PONb-protected AgNCs and sheds light on the development of new-type optical functional materials.
Keyword ：
fluorescence fluorescence macromolecules macromolecules nanoclusters nanoclusters polyoxoniobate polyoxoniobate silver silver
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| GB/T 7714 | Hong, Li-Hao , Yue, Sheng-Nan , Huang, Xing et al. Development of Stable Water-Soluble Supratomic Silver Clusters Utilizing A Polyoxoniobate-Protected Strategy: Giant Core-Shell-Type Ag8@Nb162 Fluorescent Nanocluster [J]. | ANGEWANDTE CHEMIE-INTERNATIONAL EDITION , 2024 , 63 (29) . |
| MLA | Hong, Li-Hao et al. "Development of Stable Water-Soluble Supratomic Silver Clusters Utilizing A Polyoxoniobate-Protected Strategy: Giant Core-Shell-Type Ag8@Nb162 Fluorescent Nanocluster" . | ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 63 . 29 (2024) . |
| APA | Hong, Li-Hao , Yue, Sheng-Nan , Huang, Xing , Sun, Cai , Cai, Ping-Wei , Sun, Yan-Qiong et al. Development of Stable Water-Soluble Supratomic Silver Clusters Utilizing A Polyoxoniobate-Protected Strategy: Giant Core-Shell-Type Ag8@Nb162 Fluorescent Nanocluster . | ANGEWANDTE CHEMIE-INTERNATIONAL EDITION , 2024 , 63 (29) . |
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The development of core-shell nanoclusters with controllable composition is of utmost importance as the material properties depend on their constituent elements. However, precisely tuning their compositions at the atomic scale is not easily achieved because of the difficulty of using limited macroscopic synthetic methods for atomic-level modulation. In this work, we report an interesting example of precisely regu-lating the core composition of an inorganic core-shell-type cobalt polyoxoniobate [Co26Nb36O140]32- by controlling reaction conditions, in which the inner Co-core composition could be tune while retaining the outer Nb-shell composition of resulting product, leading to a series of isostructural species with a general formula of {Co26-nNb36 +nO140} ( n = 0-2). These rare species not only can display good powder and single-crystal proton conductivities, but also might provide helpful and atomic-level insights into the syntheses, structures and composition modifications of inorganic amorphous core-shell heterometal oxide nanoparticles.(c) 2023 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
Keyword ：
Atomic-level modulation Atomic-level modulation Core-shell Core-shell Nanocluster Nanocluster Polyoxoniobate Polyoxoniobate Proton conduction Proton conduction
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| GB/T 7714 | Guo, Zheng-Wei , Chen, Yi , Chen, Zhe-Hong et al. Precisely manipulation of core composition of core-shell-type cobalt polyoxoniobates and proton conduction study [J]. | CHINESE CHEMICAL LETTERS , 2024 , 35 (1) . |
| MLA | Guo, Zheng-Wei et al. "Precisely manipulation of core composition of core-shell-type cobalt polyoxoniobates and proton conduction study" . | CHINESE CHEMICAL LETTERS 35 . 1 (2024) . |
| APA | Guo, Zheng-Wei , Chen, Yi , Chen, Zhe-Hong , Li, Xin-Xiong , Zheng, Shou-Tian . Precisely manipulation of core composition of core-shell-type cobalt polyoxoniobates and proton conduction study . | CHINESE CHEMICAL LETTERS , 2024 , 35 (1) . |
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A new inorganic-organic hybrid polyoxoboroniobate {H4K2[Cu(cis-en)(2)(H2O)](9)[Cu(cis-en)(2)](6)[Cd-2(cis-en)(2)(trans-en)][LiB2Nb29O86](2)79H(2)O} (1, en = ethylenediamine), is built from pagoda-shaped {LiB2Nb29O86} clusters, linear {Cd-2(cis-en)(2)(trans-en)} bridging units, and copper-amine complexes. The {LiB2Nb29O86} cluster represents the first example of combining oxoboron clusters with polyoxoniobate clusters (PONbs). It consists of an unusual HPONb fragment {LiNb18O54}, a fused-ring structural boroniobate cluster {B2Nb5O13}, and a classical Lindqvist {Nb6O19} fragment. The {Cd-2(cis-en)(2)(trans-en)} and [Cu(cis-en)(2)](2+) complexes link the pagoda-shaped {LiB2Nb29O86} clusters into 1D infinite ladder chains. This is the first instance of simultaneous coordination of the cis-en and trans-en ligands with a single metal cation in the inorganic-organic hybrid PONb family. Furthermore, 1 exhibits good proton conductivity.
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| GB/T 7714 | Yu, Hao , Lin, Yu-Diao , Sun, Yan-Qiong et al. A Rare Inorganic-Organic Hybrid Polyoxoboroniobate Based on Pagoda-Shaped {LiB2Nb29O86} Clusters and {Cd2(cis-en)2(trans-en)} Complexes [J]. | INORGANIC CHEMISTRY , 2024 , 63 (38) : 17351-17356 . |
| MLA | Yu, Hao et al. "A Rare Inorganic-Organic Hybrid Polyoxoboroniobate Based on Pagoda-Shaped {LiB2Nb29O86} Clusters and {Cd2(cis-en)2(trans-en)} Complexes" . | INORGANIC CHEMISTRY 63 . 38 (2024) : 17351-17356 . |
| APA | Yu, Hao , Lin, Yu-Diao , Sun, Yan-Qiong , Zheng, Shou-Tian . A Rare Inorganic-Organic Hybrid Polyoxoboroniobate Based on Pagoda-Shaped {LiB2Nb29O86} Clusters and {Cd2(cis-en)2(trans-en)} Complexes . | INORGANIC CHEMISTRY , 2024 , 63 (38) , 17351-17356 . |
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