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Polyoxometalates 2023, 2(1): 9140017 https://doi.org/10.26599/POM.2022.9140017
Review Article | Open Access | Issue | Published: 30 December 2022

State-of-the-art advances in the syntheses, structures, and applications of polyoxometalate-based metal–organic frameworks

Show Author's Information Yan Zhang1,2,  Yifan Liu1,  Dan Wang1,  Jiancai Liu1( ),  Junwei Zhao1 ( ),  Lijuan Chen1 ( )
Henan Key Laboratory of Polyoxometalate Chemistry, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, China
Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, China
Keywords:
metal–organic framework, polyoxometalate, multifunctional application
Cite this article:
Zhang Y, Liu Y, Wang D, et al. State-of-the-art advances in the syntheses, structures, and applications of polyoxometalate-based metal–organic frameworks. Polyoxometalates, 2023, 2(1): 9140017. https://doi.org/10.26599/POM.2022.9140017
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Abstract Full text About this article

Polyoxometalate-based metal–organic frameworks (PMOFs) as extended solids assembled from metal-oxide cluster units and metal–organic groups have drawn wide research attention in recent years due to the unique advantages of containing both polyoxometalate (POM) and metal–organic framework (MOF) units, which allow their multifunctional applications in catalysis, sensing, and energy storage. In this review, the recent progress on the syntheses, structural diversity, and potential applications of PMOFs are summarized. In terms of structure, two categories of PMOFs, POM@MOFs and POM–MOFs, are discussed. POM@MOFs are PMOFs in which the POM units are not coordinated to the MOF, whereas POM–MOFs are PMOFs in which the POM units are coordinated to the MOF. In terms of properties, some selected investigations on the application of PMOFs in catalysis, dye adsorption and degradation, chemical sensing and energy storage are covered. To conclude, a personal outlook and viewpoints on this field are presented. It is expected that this review will inspire researchers and provide helpful tips for the future rational design of function-oriented PMOFs.


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About this article

State-of-the-art advances in the syntheses, structures, and applications of polyoxometalate-based metal–organic frameworks

Show Author's information Yan Zhang1,2, Yifan Liu1, Dan Wang1, Jiancai Liu1( ), Junwei Zhao1 ( ), Lijuan Chen1 ( )
Henan Key Laboratory of Polyoxometalate Chemistry, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, China
Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, China

Abstract

Polyoxometalate-based metal–organic frameworks (PMOFs) as extended solids assembled from metal-oxide cluster units and metal–organic groups have drawn wide research attention in recent years due to the unique advantages of containing both polyoxometalate (POM) and metal–organic framework (MOF) units, which allow their multifunctional applications in catalysis, sensing, and energy storage. In this review, the recent progress on the syntheses, structural diversity, and potential applications of PMOFs are summarized. In terms of structure, two categories of PMOFs, POM@MOFs and POM–MOFs, are discussed. POM@MOFs are PMOFs in which the POM units are not coordinated to the MOF, whereas POM–MOFs are PMOFs in which the POM units are coordinated to the MOF. In terms of properties, some selected investigations on the application of PMOFs in catalysis, dye adsorption and degradation, chemical sensing and energy storage are covered. To conclude, a personal outlook and viewpoints on this field are presented. It is expected that this review will inspire researchers and provide helpful tips for the future rational design of function-oriented PMOFs.

Keywords: metal–organic framework, polyoxometalate, multifunctional application

References(190)

[1]

Li, C. F.; Mizuno, N.; Yamaguchi, K.; Suzuki, K. Self-assembly of anionic polyoxometalate-organic architectures based on lacunary phosphomolybdates and pyridyl ligands. J. Am. Chem. Soc. 2019, 141, 7687–7692.
DOI Google Scholar
[2]

Xuan, W. M.; Pow, R.; Watfa, N.; Zheng, Q.; Surman, A. J.; Long, D. L.; Cronin, L. Stereoselective assembly of gigantic chiral molybdenum blue wheels using lanthanide ions and amino acids. J. Am. Chem. Soc. 2019, 141, 1242–1250.
DOI Google Scholar
[3]

Yin, P. C.; Wu, B.; Mamontov, E.; Daemen, L. L.; Cheng, Y. Q.; Li, T.; Seifert, S.; Hong, K. L.; Bonnesen, P. V.; Keum, J. K. et al. J. X-ray and neutron scattering study of the formation of core-shell-type polyoxometalates. J. Am. Chem. Soc. 2016, 138, 2638–2643.
DOI Google Scholar
[4]

Gao, J.; Yan, J.; Beeg, S.; Long, D. L.; Cronin L. One-pot versus sequential reactions in the self-assembly of gigantic nanoscale polyoxotungstates. J. Am. Chem. Soc. 2013, 135, 1796–1805.
DOI Google Scholar
[5]

Miras, H. N.; Richmond, C. J.; Long, D. L.; Cronin, L. Solution-phase monitoring of the structural evolution of a molybdenum blue nanoring. J. Am. Chem. Soc. 2012, 134, 3816–3824.
DOI Google Scholar
[6]

Stuckart, M.; Monakhov, K. Y. Polyoxometalates as components of supramolecular assemblies. Chem. Sci. 2019, 10, 4364–4376.
DOI Google Scholar
[7]

Vilà-Nadal, L.; Cronin, L. Design and synthesis of polyoxometalate-framework materials from cluster precursors. Nat. Rev. Mater. 2017, 2, 17054.
DOI Google Scholar
[8]

Chen, W. C.; Li, H. L.; Wang, X. L.; Shao, K. Z.; Su, Z. M.; Wang, E. B. Assembly of cerium(III)-stabilized polyoxotungstate nanoclusters with SeO32−/TeO32− templates: From single polyoxoanions to inorganic hollow spheres in dilute solution. Chem.—Eur. J. 2013, 19, 11007–11015.
DOI Google Scholar
[9]

Yin, J.; Qi, L.; Wang, H. Y. Polyoxometalate-assisted synthesis of TiO2 nanoparticles and their applications in aqueous hybrid electrochemical capacitors. ACS Appl. Mater. Interfaces 2011, 3, 4315–4322.
DOI Google Scholar
[10]

Li, Y. M.; Li, H. L.; Jiang, J.; Chen, L. J.; Zhao, J. W. Three types of distinguishing L-alanine-decorated and rare-earth-incorporated arsenotungstate hybrids prepared in a facile one-step assembly strategy. Inorg. Chem. 2019, 58, 3479–3491.
DOI Google Scholar
[11]

Sun, H.; Yin, H. Q.; Shi, W. X.; Yang, L. L.; Guo, X. W.; Lin, H.; Zhang, J. W.; Lu, T. B.; Zhang, Z. M. Porous β-FeOOH nanotube stabilizing Au single atom for high-efficiency nitrogen fixation. Nano Res. 2022, 15, 3026–3033.
DOI Google Scholar
[12]

Bassil, B. S.; Mal, S. S.; Dickman, M. H.; Kortz, U.; Oelrich, H.; Walder, L. 6-Peroxo-6-zirconium crown and its hafnium analogue embedded in a triangular polyanion:[M6(O2)6(OH)6(γ-SiW10O36)3]18- (M = Zr, Hf). J. J. Am. Chem. Soc. 2008, 130, 6696–6697.
DOI Google Scholar
[13]

Liu, Z. J.; Wang, X. L.; Qin, C.; Zhang, Z. M.; Li, Y. G.; Chen, W. L.; Wang, E. B. Polyoxometalate-assisted synthesis of transition-metal cubane clusters as artificial mimics of the oxygen-evolving center of photosystem II. Coord. Chem. Rev. 2016, 313, 94–110.
DOI Google Scholar
[14]

Han, X. B.; Li, Y. G.; Zhang, Z. M.; Tan, H. Q.; Lu, Y.; Wang, E. B. Polyoxometalate-based nickel clusters as visible light-driven water oxidation catalysts. J. Am. Chem. Soc. 2015, 137, 5486–5493.
DOI Google Scholar
[15]

Huang, L.; Wang, S. S.; Zhao, J. W.; Cheng, L.; Yang, G. Y. Synergistic combination of multi-ZrIV cations and lacunary Keggin germanotungstates leading to a gigantic Zr24-cluster-substituted polyoxometalate. J. Am. Chem. Soc. 2014, 136, 7637–7642.
DOI Google Scholar
[16]

Liu, J. C.; Han, Q.; Chen, L. J.; Zhao, J. W.; Streb, C.; Song, Y. F. Aggregation of giant cerium-bismuth tungstate clusters into a 3D porous framework with high proton conductivity. Angew. Chem., Int. Ed. 2018, 57, 8416–8420.
DOI Google Scholar
[17]

Liao, T.; Kou, L. Z.; Du, A. J.; Gu, Y. T.; Sun, Z. Q. Simplest MOF units for effective photodriven hydrogen evolution reaction. J. Am. Chem. Soc. 2018, 140, 9159–9166.
DOI Google Scholar
[18]

Wang, X. L.; Xiao, H.; Li, A.; Li, Z.; Liu, S. J.; Zhang, Q. H.; Gong, Y.; Zheng, L. R.; Zhu, Y. Q.; Chen, C. et al. Constructing NiCo/Fe3O4 heteroparticles within MOF-74 for efficient oxygen evolution reactions. J. Am. Chem. Soc. 2018, 140, 15336–15341.
DOI Google Scholar
[19]

Zou, L. L.; Hou, C. C.; Liu, Z.; Pang, H.; Xu, Q. Superlong single-crystal metal-organic framework nanotubes. J. Am. Chem. Soc. 2018, 140, 15393–15401.
DOI Google Scholar
[20]

Li, B.; Zhao, Y. M.; Kirchon, A.; Pang, J. D.; Yang, X. Y.; Zhuang, G. L.; Zhou, H. C. Unconventional method for fabricating valence tautomeric materials: Integrating redox center within a metal-organic framework. J. Am. Chem. Soc. 2019, 141, 6822–6826.
DOI Google Scholar
[21]

Yang, H. J.; Peng, F.; Dang, C.; Wang, Y.; Hu, D. D.; Zhao, X.; Feng, P. Y.; Bu, X. H. Ligand charge separation to build highly stable quasi-isomer of MOF-74-Zn. J. Am. Chem. Soc. 2019, 141, 9808–9812.
DOI Google Scholar
[22]

Miras, H. N.; Vilà-Nadal, L.; Cronin, L. Polyoxometalate based open-frameworks (POM-OFs). Chem. Soc. Rev. 2014, 43, 5679–5699.
DOI Google Scholar
[23]

Du, D. Y.; Qin, J. S.; Li, S. L.; Su, Z. M.; Lan, Y. Q. Recent advances in porous polyoxometalate-based metal-organic framework materials. Chem. Soc. Rev. 2014, 43, 4615–4632.
DOI Google Scholar
[24]

Dolbecq, A.; Dumas, E.; Mayer, C. R.; Mialane, P. Hybrid organic-inorganic polyoxometalate compounds: From structural diversity to applications. Chem. Rev. 2010, 110, 6009–6048.
DOI Google Scholar
[25]

He, W. W.; Li, S. L.; Zang, H. Y.; Yang, G. S.; Zhang, S. R.; Su, Z. M.; Lan, Y. Q. Entangled structures in polyoxometalate-based coordination polymers. Coord. Chem. Rev. 2014, 279, 141–160.
DOI Google Scholar
[26]

Yu, R. M.; Kuang, X. F.; Wu, X. Y.; Lu, C. Z.; Donahue, J. P. Stabilization and immobilization of polyoxometalates in porous coordination polymers through host-guest interactions. Coord. Chem. Rev. 2009, 253, 2872–2890.
DOI Google Scholar
[27]

Férey, G.; Mellot-Draznieks, C.; Serre, C.; Millange, F.; Dutour, J.; Surblé, S.; Margiolaki, I. A chromium terephthalate-based solid with unusually large pore volumes and surface area. Science 2005, 309, 2040–2042.
DOI Google Scholar
[28]

Li, X. X.; Zhao, D.; Zheng, S. T. Recent advances in POM-organic frameworks and POM-organic polyhedra. Coord. Chem. Rev. 2019, 397, 220–240.
DOI Google Scholar
[29]

Cooper, E. R.; Andrews, C. D.; Wheatley, P. S.; Webb, P. B.; Wormald, P.; Morris, R. E. Ionic liquids and eutectic mixtures as solvent and template in synthesis of zeolite analogues. Nature 2004, 430, 1012–1016.
DOI Google Scholar
[30]

Aidoudi, F. H.; Aldous, D. W.; Goff, R. J.; Slawin, A. M. Z.; Attfield, J. P.; Morris, R. E.; Lightfoot, P. An ionothermally prepared S = 1/2 vanadium oxyfluoride Kagome lattice. Nat. Chem. 2011, 3, 801–806.
DOI Google Scholar
[31]

An, H. Y.; Wang, E. B.; Xiao, D. R.; Li, Y. G.; Su, Z. M.; Xu, L. Chiral 3D architectures with helical channels constructed from polyoxometalate clusters and copper-amino acid complexes. Angew. Chem., Int. Ed. 2006, 45, 904–908.
DOI Google Scholar
[32]

An, H. Y.; Wang, E. B.; Li, Y. G.; Zhang, Z. M.; Xu, L. A functionalized polyoxometalate by hexanuclear copper-amino acid coordination complexes. Inorg. Chem. Commun. 2007, 10, 299–302.
DOI Google Scholar
[33]

Cao, R. G.; Liu, S. X.; Liu, Y.; Tang, Q.; Wang, L.; Xie, L. H.; Su, Z. M. Organic-inorganic hybrids constructed by Anderson-type polyoxoanions and copper coordination complexes. J. Solid State Chem. 2009, 182, 49–54.
DOI Google Scholar
[34]

Pang, H. J.; Zhang, C. J.; Peng, J.; Wang, Y. H.; Sha, J. Q.; Tian, A. X.; Zhang, P. P.; Chen, Y.; Zhu, M.; Su, Z. M. Two new helical compounds based on pitch-tunable Keggin clusters. Eur. J. Inorg. Chem. 2009, 2009, 5175–5180.
DOI Google Scholar
[35]

Du, D. Y.; Qin, J. S.; Wang, T. T.; Li, S. L.; Su, Z. M.; Shao, K. Z.; Lan, Y. Q.; Wang, X. L.; Wang, E. B. Polyoxometalate-based crystalline tubular microreactor: Redox-active inorganic-organic hybrid materials producing gold nanoparticles and catalytic properties. Chem. Sci. 2012, 3, 705–710.
DOI Google Scholar
[36]

Zhao, J. W.; Li, Y. Z.; Chen, L. J.; Yang, G. Y. Research progress on polyoxometalate-based transition-metal-rare-earth heterometallic derived materials: Synthetic strategies, structural overview and functional applications. Chem. Commun. 2016, 52, 4418–4445.
DOI Google Scholar
[37]

Bassil, B. S.; Kortz, U. Recent advances in lanthanide-containing polyoxotungstates. Z. Anorg. Allg. Chem. 2010, 636, 2222–2231.
DOI Google Scholar
[38]

Li, H. L.; Liu, Y. J.; Liu, J. L.; Chen, L. J.; Zhao, J. W.; Yang, G. Y. Structural transformation from dimerization to tetramerization of serine-decorated rare-earth-incorporated arsenotungstates induced by the usage of rare-earth salts. Chem.—Eur. J. 2017, 23, 2673–2689.
DOI Google Scholar
[39]

Burkholder, E.; Golub, V.; O’Connor, C. J.; Zubieta, J. Solid-state coordination chemistry of the oxomolybdate-organodiphosphonate/nickel-organoimine system: Structural influences of the secondary metal coordination cation and diphosphonate tether lengths. Inorg. Chem. 2004, 43, 7014–7029.
DOI Google Scholar
[40]

Liu, J. L.; Huang, M. Y.; Hua, Z. Y.; Dong, Y.; Feng, Z. R.; Sun, T. D.; Chen, C. X. Polyoxometalate-based metal organic frameworks: Recent advances and challenges. ChemistrySelect 2022, 7, e202200546.
DOI Google Scholar
[41]

Han, Q. X.; He, C.; Zhao, M.; Qi, B.; Niu, J. Y.; Duan, C. Y. Engineering chiral polyoxometalate hybrid metal-organic frameworks for asymmetric dihydroxylation of olefins. J. Am. Chem. Soc. 2013, 135, 10186–10189.
DOI Google Scholar
[42]

Cui, Z. W.; Lu, J. J.; Lin, H. Y.; Luan, J.; Chang, Z. H.; Li, X. H.; Wang, X. L. Four Keggin-type polyoxometalate-based complexes derived from bis(pyrazine)-bis(amide) ligands for electrochemical sensing of multiple analytes and adsorbing dye molecules. CrystEngComm 2022, 24, 828–836.
DOI Google Scholar
[43]
Xu, H. K. ; Lu, K. B. ; Jiang, C. H. ; Wei, X. F. ; Wang, Z. F. ; Ouyang, Y. G. ; Dai, F. N. Electronic regulation of a core-shell NiSe2 catalyst by Co doping to accelerate hydrogen evolution. CrystEngComm, in press, DOI: 10.1039/D2CE01169G.
DOI
[44]

Ding, Y. X.; Zheng, Q. H.; Peng, M. T.; Chen, C.; Zou, K. F.; Dong, B. X.; Liu, W. L.; Teng, Y. L. A new ɛ-Keggin polyoxometalate-based metal-organic framework: From design and synthesis to electrochemical hydrogen evolution. Catal. Commun. 2021, 161, 106367.
DOI Google Scholar
[45]

Wang, X.; Li, H.; Lin, J. F.; Wang, C. Y.; Wang, X. L. Capped Keggin type polyoxometalate-based inorganic-organic hybrids involving in situ ligand transformation as supercapacitors and efficient electrochemical sensors for detecting Cr(VI). Inorg. Chem. 2021, 60, 19287–19296.
DOI Google Scholar
[46]

Li, K.; Liu, Y. F.; Lin, X. L.; Yang, G. P. Copper-containing polyoxometalate-based metal-organic frameworks as heterogeneous catalysts for the synthesis of N-heterocycles. Inorg. Chem. 2022, 61, 6934–6942.
DOI Google Scholar
[47]

Liu, B.; Yang, J.; Yang, G. C.; Ma, J. F. Four new three-dimensional polyoxometalate-based metal-organic frameworks constructed from [Mo6O18(O3AsPh)2]4- polyoxoanions and copper(I)-organic fragments: Syntheses, structures, electrochemistry, and photocatalysis properties. Inorg. Chem. 2013, 52, 84–94.
DOI Google Scholar
[48]

Lu, K.; Peláez, A. L.; Wu, L. C.; Cao, Y.; Zhu, C. H.; Fu, H. Ionothermal synthesis of five Keggin-type polyoxometalate-based metal-organic frameworks. Inorg. Chem. 2019, 58, 1794–1805.
DOI Google Scholar
[49]
Sun, J. M. ; Abednatanzi, S. ; Van Der Voort, P. ; Liu, Y. Y. ; Leus, K. POM@MOF hybrids: Synthesis and applications. Catalysts 2020, 10, 578.
DOI
[50]

Liu, Y. W.; Yang, X.; Miao, J.; Tang, Q.; Liu, S. M.; Shi, Z.; Liu, S. X. Polyoxometalate-functionalized metal-organic frameworks with improved water retention and uniform proton-conducting pathways in three orthogonal directions. Chem. Commun. 2014, 50, 10023–10026.
DOI Google Scholar
[51]

Du, Z. Y.; Yu, Y. Z.; Hong, Y. L.; Li, N. F.; Han, Y. M.; Cao, J. P.; Sun, Q.; Mei, H.; Xu, Y. Polyoxometalate-based metal-organic frameworks with unique high-nuclearity water clusters. ACS Appl. Mater. Interfaces 2020, 12, 57174–57181.
DOI Google Scholar
[52]

Hou, Y.; Pang, H. J.; Gómez-García, C. J.; Ma, H. Y.; Wang, X. M.; Tan, L. C. Polyoxometalate metal-organic frameworks: Keggin clusters encapsulated into silver-triazole nanocages and open frameworks with supercapacitor performance. Inorg. Chem. 2019, 58, 16028–16039.
DOI Google Scholar
[53]

Kuang, X. F.; Wu, X. Y.; Yu, R. M.; Donahue, J. P.; Huang, J. S.; Lu, C. Z. Assembly of a metal-organic framework by sextuple intercatenation of discrete adamantane-like cages. Nat. Chem. 2010, 2, 461–465.
DOI Google Scholar
[54]

Sha, J. Q.; Yang, X. Y.; Chen, Y. Y.; Zhu, P. P.; Song, Y. F.; Jiang, J. Z. Fabrication and electrochemical performance of polyoxometalate-based three-dimensional metal organic frameworks containing carbene nanocages. ACS Appl. Mater. Interfaces 2018, 10, 16660–16665.
DOI Google Scholar
[55]

Sha, J. Q.; Zhu, P. P.; Yang, X. Y.; Li, X. N.; Li, X.; Yue, M. B.; Zhou, K. F. Polyoxometalates templated metal Ag-carbene frameworks anodic material for lithium-ion batteries. Inorg. Chem. 2017, 56, 11998–12002.
DOI Google Scholar
[56]

Sha, J. Q.; Li, X.; Li, J. S.; Yang, X. Y.; Zhang, H. F.; Yue, M. B.; Zhou, K. F. Acidity considerations in the self-assembly of POM/Ag/trz-based compounds with efficient electrochemical activities in LIBs. Cryst. Growth Des. 2018, 18, 2289–2296.
DOI Google Scholar
[57]

Sha, J. Q.; Li, M. T.; Yang, X. Y.; Sheng, N.; Li, J. S.; Zhu, M. L.; Liu, G. D.; Jiang, J. Z. New route toward POM[6]catenane members for lithium-ion batteries. Cryst. Growth Des. 2017, 17, 3775–3782.
DOI Google Scholar
[58]

Yang, X. Y.; Wei, T.; Li, J. S.; Sheng, N.; Zhu, P. P.; Sha, J. Q.; Wang, T.; Lan, Y. Q. Polyoxometalate-incorporated metallapillararene/metallacalixarene metal-organic frameworks as anode materials for lithium ion batteries. Inorg. Chem. 2017, 56, 8311–8318.
DOI Google Scholar
[59]

Zhai, Q. G.; Wu, X. Y.; Chen, S. M.; Zhao, Z. G.; Lu, C. Z. Construction of Ag/1,2,4-triazole/polyoxometalates hybrid family varying from diverse supramolecular assemblies to 3-D rod-packing framework. Inorg. Chem. 2007, 46, 5046–5058.
DOI Google Scholar
[60]

Paille, G.; Gomez-Mingot, M.; Roch-Marchal, C.; Lassalle-Kaiser, B.; Mialane, P.; Fontecave, M.; Mellot-Draznieks, C.; Dolbecq, A. A fully noble metal-free photosystem based on cobalt-polyoxometalates immobilized in a porphyrinic metal-organic framework for water oxidation. J. Am. Chem. Soc. 2018, 140, 3613–3618.
DOI Google Scholar
[61]

Wang, K. P.; Yu, K.; Lv, J. H.; Zhang, M. L.; Meng, F. X.; Zhou, B. B. A host-guest supercapacitor electrode material based on a mixed hexa-transition metal sandwiched arsenotungstate chain and three-dimensional supramolecular metal-organic networks with one-dimensional cavities. Inorg. Chem. 2019, 58, 7947–7957.
DOI Google Scholar
[62]

Lan, G. X.; Ni, K. Y.; Veroneau, S. S.; Luo, T. K.; You, E.; Lin, W. B. Nanoscale metal-organic framework hierarchically combines high-Z components for multifarious radio-enhancement. J. Am. Chem. Soc. 2019, 141, 6859–6863.
DOI Google Scholar
[63]

Sun, W. L.; An, B. W.; Qi, B.; Liu, T.; Jin, M.; Duan, C. Y. Dual-excitation polyoxometalate-based frameworks for one-pot light-driven hydrogen evolution and oxidative dehydrogenation. ACS Appl. Mater. Interfaces 2018, 10, 13462–13469.
DOI Google Scholar
[64]

Yang, Y.; Liu, S. X.; Li, C. C.; Li, S. J.; Ren, G. J.; Wei, F.; Tang, Q. A metal-organic framework based on Wells-Dawson polyoxometalates [As2W18O62]6- template. Inorg. Chem. Commun. 2012, 17, 54–57.
DOI Google Scholar
[65]

Zhang, L. J.; Wang, X.; Yang, P. Z.; Tong, N. A lindquist-type polyoxometalate-based metal-organic framework as electrochemical sensor and efficient catalyst for selective oxidation of thioether. Inorg. Chim. Acta 2022, 542, 121125.
DOI Google Scholar
[66]

Shi, D. Y.; Zheng, R.; Liu, C. S.; Chen, D. M.; Zhao, J. W.; Du, M. Dual-functionalized mixed Keggin- and Lindqvist-type Cu24-based POM@MOF for visible-light-driven H2 and O2 evolution. Inorg. Chem. 2019, 58, 7229–7235.
DOI Google Scholar
[67]

Shi, D. Y.; He, C.; Sun, W. L.; Ming, Z.; Meng, C. G.; Duan, C. Y. A photosensitizing decatungstate-based MOF as heterogeneous photocatalyst for the selective C-H alkylation of aliphatic nitriles. Chem. Commun. 2016, 52, 4714–4717.
DOI Google Scholar
[68]

Li, Y. Y.; Leng, C. L.; Zhao, J. W.; Chen, S. D.; Ma, P. T.; Chen, L. J. A six-connected 3-D framework [enH2]2[Cu(en)2]3[H2W12O42]·6H2O constructed from paratungstate-based polyoxometalate units. Inorg. Chem. Commun. 2012, 25, 35–38.
DOI Google Scholar
[69]

Lin, B. Z.; Chen, Y. M.; Liu, P. D. A new polymeric chain formed by paradodecatungstate clusters and [Cu(en)2]2+ complexes: Hydrothermal synthesis and characterization of [Cu(en)2]3[{Cu(en)2}2(H2W12O42)]·12H2O. Dalton Trans. 2003, 2474–2477
DOI Google Scholar
[70]

Zhu, P. P.; Sheng, N.; Li, M. T.; Li, J. S.; Liu, G. D.; Yang, X. Y.; Sha, J. Q.; Zhu, M. L.; Jiang, J. Z. Fabrication and electrochemical performance of unprecedented POM-based metal-carbene frameworks. J. Mater. Chem. A 2017, 5, 17920–17925.
DOI Google Scholar
[71]

Roy, S.; Vemuri, V.; Maiti, S.; Manoj, K. S.; Subbarao, U.; Peter, S. C. Two Keggin-based isostructural POMOF hybrids: Synthesis, crystal structure, and catalytic properties. Inorg. Chem. 2018, 57, 12078–12092.
DOI Google Scholar
[72]

Yang, P.; Zhao, W. L.; Shkurenko, A.; Belmabkhout, Y.; Eddaoudi, M.; Dong, X. C.; Alshareef, H. N.; Khashab, N. M. Polyoxometalate-cyclodextrin metal-organic frameworks: From tunable structure to customized storage functionality. J. Am. Chem. Soc. 2019, 141, 1847–1851.
DOI Google Scholar
[73]

Xiong, Y. L.; Yu, M. Y.; Guo, T. T.; Yang, J.; Ma, J. F. A nanosized propeller-like polyoxometalate-linked copper(I)-resorcin[4]arene for efficient catalysis. Inorg. Chem. 2020, 59, 15402–15409.
DOI Google Scholar
[74]

Dong, B. X.; Bu, F. Y.; Wu, Y. C.; Zhao, J.; Teng, Y. L.; Liu, W. L.; Li, Z. W. Construction of (3, 4)-connected polyoxometalate-based metal-organic frameworks (POMOFs) from triangular carboxylate and tetrahedral Zn4-ε-Keggin. Cryst. Growth Des. 2017, 17, 5309–5317.
DOI Google Scholar
[75]

Yu, H. H.; Cui, X. B.; Cui, J. W.; Kong, L.; Duan, W. J.; Xu, J. Q.; Wang, T. G. Hydrothermal synthesis and structural characterization of the first mixed molybdenum-tungsten capped-Keggin polyoxometal complex: {[Co(dien)]4[(AsVO4)MoV8WVI4O33(µ2-OH)3]}·2H2O. Dalton Trans. 2008, 195–197
DOI Google Scholar
[76]

Dolbecq, A.; Mialane, P.; Sécheresse, F.; Keita, B.; Nadjo, L. Functionalized polyoxometalates with covalently linked bisphosphonate, N-donor or carboxylate ligands: From electrocatalytic to optical properties. Chem. Commun. 2012, 48, 8299–8316.
DOI Google Scholar
[77]

Dolbecq, A.; Mellot-Draznieks, C.; Mialane, P.; Marrot, J.; Férey, G.; Sécheresse, F. Hybrid 2D and 3D frameworks based on ε-Keggin polyoxometallates: Experiment and simulation. Eur. J. Inorg. Chem. 2005, 2005, 3009–3018.
DOI Google Scholar
[78]

Cui, X. B.; Zheng, S. T.; Yang, G. Y. First nickel(II) cation inclusion within the mixed-valence polyoxomolybdate capped with four NiII(en)(H2O) groups: Hydrothermal synthesis and structure of [MoV8MoVI4O30(μ2-OH)6(NiIIO4){NiII(en)(H2O)}4]. Z. Anorg. Allg. Chem. 2005, 631, 642–644.
DOI Google Scholar
[79]

Rodriguez-Albelo, L. M.; Ruiz-Salvador, A. R.; Sampieri, A.; Lewis, D. W.; Gómez, A.; Nohra, B.; Mialane, P.; Marrot, J.; Sécheresse, F.; Mellot-Draznieks, C. et al. Zeolitic polyoxometalate-based metal-organic frameworks (Z-POMOFs): Computational evaluation of hypothetical polymorphs and the successful targeted synthesis of the redox-active Z-POMOF1. J. Am. Chem. Soc. 2009, 131, 16078–16087.
DOI Google Scholar
[80]

Wang, Y. Y.; Zhang, M.; Li, S. L.; Zhang, S. R.; Xie, W.; Qin, J. S.; Su, Z. M.; Lan, Y. Q. Diamondoid-structured polymolybdate-based metal-organic frameworks as high-capacity anodes for lithium-ion batteries. Chem. Commun. 2017, 53, 5204–5207.
DOI Google Scholar
[81]

Nohra, B.; El Moll, H.; Albelo, L. M. R.; Mialane, P.; Marrot, J.; Mellot-Draznieks, C.; O’Keeffe, M.; Biboum, R. N.; Lemaire, J.; Keita, B. et al. Polyoxometalate-based metal organic frameworks (POMOFs): Structural trends, energetics, and high electrocatalytic efficiency for hydrogen evolution reaction. J. Am. Chem. Soc. 2011, 133, 13363–13374.
DOI Google Scholar
[82]

Huang, Q.; Wei, T.; Zhang, M.; Dong, L. Z.; Zhang, A. M.; Li, S. L.; Liu, W. J.; Liu, J.; Lan, Y. Q. A highly stable polyoxometalate-based metal-organic framework with π-π stacking for enhancing lithium ion battery performance. J. Mater. Chem. A 2017, 5, 8477–8483.
DOI Google Scholar
[83]

Zhang, H. L.; Liu, W.; Li, A.; Zhang, D.; Li, X. Y.; Zhai, F. W.; Chen, L. H.; Chen, L.; Wang, Y. L.; Wang, S. Three mechanisms in one material: Uranium capture by a polyoxometalate-organic framework through combined complexation, chemical reduction, and photocatalytic reduction. Angew. Chem., Int. Ed. 2019, 58, 16110–16114.
DOI Google Scholar
[84]

Huang, Q.; Liu, J.; Feng, L.; Wang, Q.; Guan, W.; Dong, L. Z.; Zhang, L.; Yan, L. K.; Lan, Y. Q.; Zhou, H. C. Multielectron transportation of polyoxometalate-grafted metalloporphyrin coordination frameworks for selective CO2-to-CH4 photoconversion. Natl. Sci. Rev. 2020, 7, 53–63.
DOI Google Scholar
[85]

Cheng, W. W.; Shen, F. C.; Xue, Y. S.; Luo, X. M.; Fang, M.; Lan, Y. Q.; Xu, Y. A pair of rare three-dimensional chiral polyoxometalate-based metal-organic framework enantiomers featuring superior performance as the anode of lithium-ion battery. ACS Appl. Energy Mater. 2018, 1, 4931–4938.
DOI Google Scholar
[86]

Huang, P.; Qin, C.; Wang, X. L.; Sun, C. Y.; Yang, G. S.; Shao, K. Z.; Jiao, Y. Q.; Zhou, K.; Su, Z. M. An unprecedented organic-inorganic hybrid based on the first {Nb10V4O40(OH)2}12- clusters and copper cations. Chem. Commun. 2012, 48, 103–105.
DOI Google Scholar
[87]

Guo, G. L.; Xu, Y. Q.; Cao, J.; Hu, C. W. An unprecedented vanadoniobate cluster with ‘trans-vanadium’ bicapped Keggin-type {VNb12O40(VO)2}. Chem. Commun. 2011, 47, 9411–9413.
DOI Google Scholar
[88]

Shen, J. Q.; Zhang, Y.; Zhang, Z. M.; Li, Y. G.; Gao, Y. Q.; Wang, E. B. Polyoxoniobate-based 3D framework materials with photocatalytic hydrogen evolution activity. Chem. Commun. 2014, 50, 6017–6019.
DOI Google Scholar
[89]

Wang, Y. J.; Zhou, Y. Y.; Hao, H. G.; Song, M.; Zhang, N.; Yao, S.; Yan, J. H.; Zhang, Z. M.; Lu, T. B. Capped polyoxometalate pillars between metal-organic layers for transferring a supramolecular structure into a covalent 3D framework. Inorg. Chem. 2018, 57, 1342–1349.
DOI Google Scholar
[90]

Zhang, R. T.; Xiao, H. P.; Li, Z.; Wang, M.; Xie, Y. F.; Ye, Y. D.; Li, X. X.; Zheng, S. T. Two highly stable inorganic-organic hybrid 3D frameworks based on Cu-Ln incorporated polyoxometalates for selective dye removal and proton conduction. CrystEngComm 2021, 23, 2973–2981.
DOI Google Scholar
[91]

Han, Q. X.; Sun, X. P.; Li, J.; Ma, P. T.; Niu, J. Y. Novel isopolyoxotungstate [H2W11O38]8- based metal organic framework: As lewis acid catalyst for cyanosilylation of aromatic aldehydes. Inorg. Chem. 2014, 53, 6107–6112.
DOI Google Scholar
[92]

Shi, D. Y.; He, C.; Qi, B.; Chen, C.; Niu, J. Y.; Duan, C. Y. Merging of the photocatalysis and copper catalysis in metal-organic frameworks for oxidative C-C bond formation. Chem. Sci. 2015, 6, 1035–1042.
DOI Google Scholar
[93]

Jiao, J. C.; Yan, X. M.; Xing, S. Z.; Zhang, T.; Han, Q. X. Design of a polyoxometalate-based metal-organic framework for photocatalytic C(sp3)-H oxidation of toluene. Inorg. Chem. 2022, 61, 2421–2427.
DOI Google Scholar
[94]

Si, C.; Liu, F.; Yan, X. M.; Xu, J. B.; Niu, G. Q.; Han, Q. X. Designing a polyoxometalate-incorporated metal-organic framework for reduction of nitroarenes to anilines by sequential proton-coupled electron transfers. Inorg. Chem. 2022, 61, 5335–5342.
DOI Google Scholar
[95]

Jiao, J. C.; Sun, H.; Si, C.; Xu, J. B.; Zhang, T.; Han, Q. X. Photocatalytic multielectron reduction of nitroarenes to anilines by utilizing an electron-storable polyoxometalate-based metal-organic framework. ACS Appl. Mater. Interfaces 2022, 14, 16386–16393.
DOI Google Scholar
[96]

Wang, J. P.; Duan, X. Y.; Du, X. D.; Niu, J. Y. Novel rare earth germanotungstates and organic hybrid derivatives:  Synthesis and structures of M/[α-GeW11O39] (M = Nd, Sm, Y, Yb) and Sm/[α-GeW11O39](DMSO). Cryst. Growth Des. 2006, 6, 2266–2270.
DOI Google Scholar
[97]

Wang, J. P.; Zhao, J. W.; Duan, X. Y.; Niu, J. Y. Syntheses and structures of one- and two-dimensional organic-inorganic hybrid rare earth derivatives based on monovacant Keggin-type polyoxotungstates. Cryst. Growth Des. 2006, 6, 507–513.
DOI Google Scholar
[98]

An, H. Y.; Han, Z. B.; Xu, T. Q. Three-dimensional architectures based on lanthanide-substituted double-Keggin-type polyoxometalates and lanthanide cations or lanthanide-organic complexes. Inorg. Chem. 2010, 49, 11403–11414.
DOI Google Scholar
[99]

An, H. Y.; Zhang, H.; Chen, Z. F.; Li, Y. G.; Liu, X.; Chen, H. A series of three-dimensional architectures constructed from lanthanide-substituted polyoxometalosilicates and lanthanide cations or lanthanide-organic complexes as linkers. Dalton Trans. 2012, 41, 8390–8400.
DOI Google Scholar
[100]

Wang, Z. W.; Zhao, Q.; Chen, C. A.; Sun, J. J.; Lv, H. J.; Yang, G. Y. Chiral {Ni6PW9} cluster-organic framework: Synthesis, structure, and properties. Inorg. Chem. 2022, 61, 7477–7483.
DOI Google Scholar
[101]

Zhang, Z.; Wang, Y. L.; Li, H. L.; Sun, K. N.; Yang, G. Y. Syntheses, structures and properties of three organic-inorganic hybrid polyoxotungstates constructed from {Ni6PW9} building blocks: From isolated clusters to 2-D layers. CrystEngComm 2019, 21, 2641–2647.
DOI Google Scholar
[102]

Zheng, S. T.; Zhang, J.; Yang, G. Y. Designed synthesis of POM-organic frameworks from {Ni6PW9} building blocks under hydrothermal conditions. Angew. Chem., Int. Ed. 2008, 47, 3909–3913.
DOI Google Scholar
[103]

Chen, Y. H.; Sun, L. H.; Chang, S. Z.; Chen, L. J.; Zhao, J. W. Synergistic effect between different coordination geometries of lanthanides and various coordination modes of 2-picolinic acid ligands tuning three types of rare 3d-4f heterometallic tungstoantimonates. Inorg. Chem. 2018, 57, 15079–15092.
DOI Google Scholar
[104]

Wang, X. L.; Zhang, R.; Wang, X.; Lin, H. Y.; Liu, G. C. An effective strategy to construct novel polyoxometalate-based hybrids by deliberately controlling organic ligand transformation in situ. Inorg. Chem. 2016, 55, 6384–6393.
DOI Google Scholar
[105]

Li, D. D.; Xu, Q. F.; Li, Y. G.; Qiu, Y. T.; Ma, P. T.; Niu, J. Y.; Wang, J. P. A stable polyoxometalate-based metal-organic framework as highly efficient heterogeneous catalyst for oxidation of alcohols. Inorg. Chem. 2019, 58, 4945–4953.
DOI Google Scholar
[106]

Zhu, P. P.; Sun, L. J.; Sheng, N.; Sha, J. Q.; Liu, G. D.; Yu, L.; Qiu, H. B.; Li, S. X. Tuning the helical structures of Wells-Dawson polyoxometalate based hybrid compounds by using isomeric ligands. Cryst. Growth Des. 2016, 16, 3215–3223.
DOI Google Scholar
[107]

Wang, X. Q.; Liu, S. X.; Liu, Y. W.; He, D. F.; Li, N.; Miao, J.; Ji, Y. J.; Yang, G. Y. Planar {Ni6} cluster-containing polyoxometalate-based inorganic-organic hybrid compound and its extended structure. Inorg. Chem. 2014, 53, 13130–13135.
DOI Google Scholar
[108]

Zheng, S. T.; Yuan, D. Q.; Jia, H. P.; Zhang, J.; Yang, G. Y. Combination between lacunary polyoxometalates and high-nuclear transition metal clusters under hydrothermal conditions: I. From isolated cluster to 1-D chain. Chem. Commun. 2007, 1858–1860
DOI Google Scholar
[109]

Zhao, J. W.; Jia, H. P.; Zhang, J.; Zheng, S. T.; Yang, G. Y. A combination of lacunary polyoxometalates and high-nuclear transition-metal clusters under hydrothermal conditions. Part II: From double cluster, dimer, and tetramer to three-dimensional frameworks. Chem.—Eur. J. 2007, 13, 10030–10045.
DOI Google Scholar
[110]

Reinoso, S.; Dickman, M. H.; Kortz, U. A novel hexatungstate fragment stabilized by dimethyltin groups: [{(CH3)2Sn}2(W6O22)]4-. Inorg. Chem. 2006, 45, 10422–10424.
DOI Google Scholar
[111]

Chen, W. C.; Qin, C.; Li, Y. G.; Zang, H. Y.; Shao, K. Z.; Su, Z. M.; Wang, E. B.; Liu, H. S. Assembly of tetrameric dimethyltin-functionalized selenotungstates: From nanoclusters to one-dimensional chains. Chem. Commun. 2015, 51, 2433–2436.
DOI Google Scholar
[112]

Li, X. X.; Wang, Y. X.; Wang, R. H.; Cui, C. Y.; Tian, C. B.; Yang, G. Y. Designed assembly of heterometallic cluster organic frameworks based on Anderson-type polyoxometalate clusters. Angew. Chem., Int. Ed. 2016, 55, 6462–6466.
DOI Google Scholar
[113]

Li, X. X.; Deng, C. C.; Zhao, D.; Yu, H.; Zeng, Q. X.; Zheng, S. T. Composite cluster-organic frameworks based on polyoxometalates and copper/cobalt-oxygen clusters. Dalton Trans. 2018, 47, 16408–16412.
DOI Google Scholar
[114]

Zhu, M. C.; Huang, Y. Y.; Ma, J. P.; Hu, S. M.; Wang, Y.; Guo, J.; Zhao, Y. X.; Wang, L. S. Coordination polymers based on organic-inorganic hybrid rigid rod comprising a backbone of Anderson-Evans POMs. Cryst. Growth Des. 2019, 19, 925–931.
DOI Google Scholar
[115]

Ying, J.; Chen, Y. G.; Wang, X. Y. A series of 0D to 3D Anderson-type polyoxometalate-based compounds obtained under ambient and hydrothermal conditions. CrystEngComm 2019, 21, 1168–1179.
DOI Google Scholar
[116]

Sun, C. X.; Zhang, Y. P.; Ying, J.; Jin, L.; Tian, A. X.; Wang, X. L. A series of POM compounds constructed using a flexible ligand containing three coordination groups: Electrocatalytic and photocatalytic reduction and amperometric detection of Cr(VI). New J. Chem. 2022, 46, 2798–2807.
DOI Google Scholar
[117]

Zhang, Y.; Wang, X.; Wang, Y.; Xu, N.; Wang, X. L. Cobalt complexes tuned by Anderson-type polyoxometalates and bis-amide derivative ligands featuring a ‘V’-like connector for efficient ampere sensing and the visible-light catalytic reduction of Cr(VI). Dalton Trans. 2022, 51, 7109–7117.
DOI Google Scholar
[118]

Li, J. H.; Wang, X. L.; Song, G.; Lin, H. Y.; Wang, X.; Liu, G. C. Various Anderson-type polyoxometalate-based metal-organic complexes induced by diverse solvents: Assembly, structures and selective adsorption for organic dyes. Dalton Trans. 2020, 49, 1265–1275.
DOI Google Scholar
[119]

Merkel, M. P.; Anson, C. E.; Kostakis, G. E.; Powell, A. K. Taking the third route for construction of POMOFs: The first use of carboxylate-functionalized MnIII Anderson-Evans POM-hybrid linkers and lanthanide nodes. Cryst. Growth Des. 2021, 21, 3179–3190.
DOI Google Scholar
[120]

She, S.; Bian, S. T.; Hao, J.; Zhang, J. W.; Zhang, J.; Wei, Y. G. Aliphatic organoimido derivatives of polyoxometalates containing a bioactive ligand. Chem.—Eur. J. 2014, 20, 16987–16994.
DOI Google Scholar
[121]

Zhu, Y.; Yin, P. C.; Xiao, F. P.; Li, D.; Bitterlich, E.; Xiao, Z. C.; Zhang, J.; Hao, J.; Liu, T. B.; Wang, Y. et al. Bottom-up construction of POM-based macrostructures: Coordination assembled paddle-wheel macroclusters and their vesicle-like supramolecular aggregation in solution. J. Am. Chem. Soc. 2013, 135, 17155–17160.
DOI Google Scholar
[122]

Li, X. X.; Zhang, L. J.; Cui, C. Y.; Wang, R. H.; Yang, G. Y. Designed construction of cluster organic frameworks from Lindqvist-type polyoxovanadate cluster. Inorg. Chem. 2018, 57, 10323–10330.
DOI Google Scholar
[123]

Lin, L. D.; Li, Z.; Zhao, D.; Liu, J. H.; Li, X. X.; Zheng, S. T. Development of a new Lindqvist-like Fe6 cluster secondary building unit for MOFs. Chem. Commun. 2019, 55, 10729–10732.
DOI Google Scholar
[124]

Wang, X. L.; Zhang, H. X.; Wang, X.; Zhang, S.; Liu, J. H.; Lin, H. Y.; Liu, G. C. A novel two-fold interpenetrating 3D metal-organic framework based on Lindqvist-type hexamolybdate: Synthesis, structure, electrochemical and photocatalytic properties. Inorg. Chem. Commun. 2018, 88, 60–64.
DOI Google Scholar
[125]

Qu, Z. K.; Yu, K.; Zhao, Z. F.; Su, Z. H.; Sha, J. Q.; Wang, C. M.; Zhou, B. B. An organic-inorganic hybrid semiconductor material based on Lindqvist polyoxomolybdate and a tetra-nuclear copper complex containing two different ligands. Dalton Trans. 2014, 43, 6744–6751.
DOI Google Scholar
[126]

Tian, H. R.; Zhang, Z.; Dang, T. Y.; Liu, S. M.; Lu, Y.; Liu, S. X. Hollow Lindqvist-like-shaped {V6} cluster-based metal-organic framework for the highly efficient detoxification of mustard gas simulant. Inorg. Chem. 2021, 60, 840–845.
DOI Google Scholar
[127]

Qin, J. S.; Du, D. Y.; Guan, W.; Bo, X. J.; Li, Y. F.; Guo, L. P.; Su, Z. M.; Wang, Y. Y.; Lan, Y. Q.; Zhou, H. C. Ultrastable polymolybdate-based metal-organic frameworks as highly active electrocatalysts for hydrogen generation from water. J. Am. Chem. Soc. 2015, 137, 7169–7177.
DOI Google Scholar
[128]

Clemente-Juan, J. M.; Coronado, E.; Gaita-Ariño, A. Magnetic polyoxometalates: From molecular magnetism to molecular spintronics and quantum computing. Chem. Soc. Rev. 2012, 41, 7464–7478.
DOI Google Scholar
[129]

Wei, Y. Q.; Sun, C.; Chen, Q. S.; Wang, M. S.; Guo, G. C. Significant enhancement of conductance of a hybrid layered molybdate semiconductor by light or heat. Chem. Commun. 2018, 54, 14077–14080.
DOI Google Scholar
[130]

Tan, H. Q.; Li, Y. G.; Chen, W. L.; Yan, A. X.; Liu, D.; Wang, E. B. A series of [MnMo9O32]6− based solids: Homochiral transferred from adjacent polyoxoanions to one-, two-, and three-dimensional frameworks. Cryst. Growth Des. 2012, 12, 1111–1117.
DOI Google Scholar
[131]

Tanaka, S.; Annaka, M.; Sakai, K. Visible light-induced wateroxidation catalyzed by molybdenum-based polyoxometalates with mono- and dicobalt(III) cores as oxygen-evolving centers. Chem. Commun. 2012, 48, 1653–1655.
DOI Google Scholar
[132]

An, H. Y.; Hu, Y.; Wang, L.; Zhou, E. L.; Fei, F.; Su, Z. M. 3D racemic microporous frameworks and 3D chiral supramolecular architectures based on Evans-Showell-type polyoxometalates controlled by the temperature. Cryst. Growth Des. 2015, 15, 164–175.
DOI Google Scholar
[133]

Hou, Y. J.; An, H. Y.; Ding, B. J.; Li, Y. Q. Evans-Showell-type polyoxometalate constructing novel 3D inorganic architectures with alkaline earth metal linkers: Syntheses, structures and catalytic properties. Dalton Trans. 2017, 46, 8439–8450.
DOI Google Scholar
[134]

Liu, Q. Q.; Lin, H. Y.; Wang, X. L.; Wang, X.; Xu, N.; Tian, Y.; Yang, L.; Li, X. R.; Sun, J. Y. Two novel polyoxometalate-based metal-organic complexes with chiral Waugh-type [MnMo9O32]6− anions as high-efficiency catalytic oxidative desulfurization catalysts. Cryst. Growth Des. 2021, 21, 7015–7022.
DOI Google Scholar
[135]

Li, X. M.; Chen, Y. G.; Su, C. N.; Zhou, S.; Tang, Q.; Shi, T. Functionalized pentamolybdodiphosphate-based inorganic-organic hybrids: Synthesis, structure, and properties. Inorg. Chem. 2013, 52, 11422–11427.
DOI Google Scholar
[136]

Zhang, M. L.; Lv, J. H.; Yu, K.; Wang, K. P.; Meng, F. X.; Zhou, B. B. An unusual 2, 12-connected 3-D open framework based on {As2Mo6O26}-type polyoxometallate and copper-pyrazole complex. Inorg. Chem. Commun. 2018, 97, 74–78.
DOI Google Scholar
[137]

Cong, B. W.; Su, Z. H.; Zhao, Z. F.; Yu, B. Y.; Zhao, W. Q.; Xia, L.; Ma, X. J.; Zhou, B. B. Assembly of six [HxAs2Mo6O26](6−x)− cluster-based hybrid materials from 1D chains to 3D framework with multiple Cu-N complexes. CrystEngComm 2017, 19, 2739–2749.
DOI Google Scholar
[138]

Zhang, N.; Hong, L. Y.; Geng, A. F.; Yan, J. H.; Yao, S.; Zhang, Z. M. Extended structural materials constructed from sulfate-centered Preyssler-type polyoxometalate with excellent electrocatalytic property. Chin. Chem. Lett. 2018, 29, 1409–1412.
DOI Google Scholar
[139]

Li, Y. Y.; Zhao, J. W.; Wei, Q.; Yang, B. F.; He, H.; Yang, G. Y. Two organic-inorganic hybrid 3D {P5W30}-based heteropolyoxotungstates with transition-metal/Ln-carboxylate-Ln connectors. Chem.—Asian J. 2014, 9, 858–867.
DOI Google Scholar
[140]

Tian, H. R.; Liu, Y. W.; Zhang, Z.; Liu, S. M.; Dang, T. Y.; Li, X. H.; Sun, X. W.; Lu, Y.; Liu, S. X. A multicentre synergistic polyoxometalate-based metal-organic framework for one-step selective oxidative cleavage of β-O-4 lignin model compounds. Green Chem. 2020, 22, 248–255.
DOI Google Scholar
[141]

Nyman, M. Polyoxoniobate chemistry in the 21st century. Dalton Trans. 2011, 40, 8049–8058.
DOI Google Scholar
[142]

Bontchev, R. P.; Nyman, M. Evolution of polyoxoniobate cluster anions. Angew. Chem., Int. Ed. 2006, 45, 6670–6672.
DOI Google Scholar
[143]

Niu, J. Y.; Ma, P. T.; Niu, H. Y.; Li, J.; Zhao, J. W.; Song, Y.; Wang, J. P. Giant polyniobate clusters based on [Nb7O22]9− units derived from a Nb6O19 precursor. Chem.—Eur. J. 2007, 13, 8739–8748.
DOI Google Scholar
[144]

Wang, Z. L.; Tan, H. Q.; Chen, W. L.; Li, Y. G.; Wang, E. B. A copper(II)-ethylenediamine modified polyoxoniobate with photocatalytic H2 evolution activity under visible light irradiation. Dalton Trans. 2012, 41, 9882–9884.
DOI Google Scholar
[145]

Zhu, Z. K.; Lin, L. D.; Zhang, J.; Li, X. X.; Sun, Y. Q.; Zheng, S. T. A rare 4-connected neb-type 3D chiral polyoxometalate framework based on {KNb24O72} clusters. Inorg. Chem. Front. 2020, 7, 3919–3924.
DOI Google Scholar
[146]

Zhu, Z. K.; Lin, Y. Y.; Yu, H.; Li, X. X.; Zheng, S. T. Inorganic-organic hybrid polyoxoniobates: Polyoxoniobate metal complex cage and cage framework. Angew. Chem., Int. Ed. 2019, 58, 16864–16868.
DOI Google Scholar
[147]

Abramov, P. A.; Komarov, V. Y.; Pischur, D. A.; Sulyaeva, V. S.; Benassi, E.; Sokolov, M. N. Solvatomorphs of (Bu4N)2[{Ag(N2-py)}2Mo8O26]: Structure, colouration and phase transition. CrystEngComm 2021, 23, 8527–8537.
DOI Google Scholar
[148]

Li, F. C.; Li, X. L.; Tan, L. K.; Wang, J. T.; Yao, W. Z. Evans-Showell-type polyoxometalate-based metal-organic complexes with novel 3D structures constructed from flexible bis-pyrazine-bis-amide ligands and copper metals: Syntheses, structures, and fluorescence and catalytic properties. Dalton Trans. 2019, 48, 2160–2169.
DOI Google Scholar
[149]

Li, F. C.; Tan, L. K.; Li, X. L.; Kong, H. J.; Ge, L. M.; Yue, L. Y.; Han, L. F. Syntheses, structures and catalytic properties of Evans-Showell-type polyoxometalate-based 3D metal-organic complexes constructed from the semi-rigid bis(pyridylformyl)piperazine ligand and transition metals. Dalton Trans. 2019, 48, 5831–5841.
DOI Google Scholar
[150]

Lin, L. D.; Zhao, D.; Li, X. X.; Zheng, S. T. Recent advances in zeolite-like cluster organic frameworks. Chem.—Eur. J. 2019, 25, 442–453.
DOI Google Scholar
[151]

Liu, H.; Zhang, J.; Xu, X. X.; Wang, Q. A polyoxometalate-based binder-free capacitive deionization electrode for highly efficient sea water desalination. Chem.—Eur. J. 2020, 26, 4403–4409.
DOI Google Scholar
[152]

Li, X. H.; He, P.; Wang, T.; Zhang, X. W.; Chen, W. L.; Li, Y. G. Keggin-type polyoxometalate-based ZIF-67 for enhanced photocatalytic nitrogen fixation. ChemSusChem 2020, 13, 2769–2778.
DOI Google Scholar
[153]

Su, S. D.; Li, X. M.; Zhang, X.; Zhu, J. T.; Liu, G. D.; Tan, M. Y.; Wang, Y. Y.; Luo, M. Keggin-type SiW12 encapsulated in MIL-101(Cr) as efficient heterogeneous photocatalysts for nitrogen fixation reaction. J. Colloid. Interf. Sci. 2022, 61, 406–415.
DOI Google Scholar
[154]

Yu, Z. Y.; Lin, T.; Zhu, C. F.; Li, J. T.; Luo, X. T. Design of trimetallic NiMoFe hollow microspheres with polyoxometalate-based metal-organic frameworks for enhanced oxygen evolution reaction. ChemElectroChem 2021, 8, 1316–1321.
DOI Google Scholar
[155]

Wang, W.; Zhang, J.; Lin, K. F.; Dong, Y. Y.; Wang, J. Q.; Hu, B. Y.; Li, J.; Shi, Z.; Hu, Y. J.; Cao, W. et al. Construction of polyoxometalate-based material for eliminating multiple Pb-based defects and enhancing thermal stability of perovskite solar cells. Adv. Funct. Mater. 2021, 31, 2105884.
DOI Google Scholar
[156]

Dong, Y. Y.; Zhang, J.; Yang, Y. L.; Wang, J. Q.; Hu, B. Y.; Wang, W.; Cao, W.; Gai, S.; Xia, D. B.; Lin, K. F. et al. Multifunctional nanostructured host-guest POM@MOF with lead sequestration capability induced stable and efficient perovskite solar cells. Nano Energy 2022, 97, 107184.
DOI Google Scholar
[157]

Mallat, T.; Baiker, A. Oxidation of alcohols with molecular oxygen on solid catalysts. Chem. Rev. 2004, 104, 3037–3058.
DOI Google Scholar
[158]

Long, D. L.; Tsunashima, R.; Cronin, L. Polyoxometalates: Building blocks for functional nanoscale systems. Angew. Chem., Int. Ed. 2010, 49, 1736–1758.
DOI Google Scholar
[159]

Long, D. L.; Burkholder, E.; Cronin, L. Polyoxometalate clusters, nanostructures and materials: From self assembly to designer materials and devices. Chem. Soc. Rev. 2007, 36, 105–121.
DOI Google Scholar
[160]

Wang, S. S.; Yang, G. Y. Recent advances in polyoxometalate-catalyzed reactions. Chem. Rev. 2015, 115, 4893–4962.
DOI Google Scholar
[161]

Sloboda-Rozner, D.; Alsters, P. L.; Neumann, R. A water-soluble and “self-assembled” polyoxometalate as a recyclable catalyst for oxidation of alcohols in water with hydrogen peroxide. J. Am. Chem. Soc. 2003, 125, 5280–5281.
DOI Google Scholar
[162]

Liu, Y. W.; Wang, B. X.; Fu, Q.; Liu, W.; Wang, Y.; Gu, L.; Wang, D. S.; Li, Y. D. Polyoxometalate-based metal-organic framework as molecular sieve for highly selective semi-hydrogenation of acetylene on isolated single Pd atom sites. Angew. Chem., Int. Ed. 2021, 60, 22522–22528.
DOI Google Scholar
[163]

Wang, X. K.; Zhou, X. K.; Li, C.; Yao, H. X.; Zhang, C. H.; Zhou, J.; Xu, R.; Chu, L.; Wang, H. L.; Gu, M. et al. Asymmetric Co-N3P1 trifunctional catalyst with tailored electronic structures enabling boosted activities and corrosion resistance in an uninterrupted seawater splitting system. Adv. Mater. 2022, 34, 2204021.
DOI Google Scholar
[164]

Rong, C. L.; Shen, X. J.; Wang, Y.; Thomsen, L.; Zhao, T. W.; Lu, Y. B.; Lu, X. Y.; Amal, R.; Zhao, C. Electronic structure engineering of single-atom Ru sites via Co-N4 sites for bifunctional pH-universal water splitting. Adv. Mater. 2022, 34, 2110103.
DOI Google Scholar
[165]

Jung, E.; Shin, H.; Lee, B. H.; Efremov, V.; Lee, S.; Lee, H. S.; Kim, J.; Antink, W. H.; Park, S.; Lee, K. S. et al. Atomic-level tuning of Co-N-C catalyst for high-performance electrochemical H2O2 production. Nat. Mater. 2020, 19, 436–442.
DOI Google Scholar
[166]

Liu, Y. W.; Wu, X.; Li, Z.; Zhang, J.; Liu, S. X.; Liu, S. J.; Gu, L.; Zheng, L. R.; Li, J.; Wang, D. S.; Li, Y. D. Fabricating polyoxometalates-stabilized single-atom site catalysts in confined space with enhanced activity for alkynes diboration. Nat. Commun. 2021, 12, 4205.
DOI Google Scholar
[167]

Wang, Z. H.; Wang, X. F.; Tan, Z.; Song, X. Z. Polyoxometalate/metal-organic framework hybrids and their derivatives for hydrogen and oxygen evolution electrocatalysis. Mater. Today Energy 2021, 19, 100618.
DOI Google Scholar
[168]

Li, H.; Yao, S.; Wu, H. L.; Qu, J. Y.; Zhang, Z. M.; Lu, T. B.; Lin, W. B.; Wang, E. B. Charge-regulated sequential adsorption of anionic catalysts and cationic photosensitizers into metal-organic frameworks enhances photocatalytic proton reduction. Appl. Catal. B: Environ. 2018, 224, 46–52.
DOI Google Scholar
[169]

Zhang, Z. M.; Zhang, T.; Wang, C.; Lin, Z. K.; Long, L. S.; Lin, W. B. Photosensitizing metal-organic framework enabling visible-light-driven proton reduction by a Wells-Dawson-type polyoxometalate. J. Am. Chem. Soc. 2015, 137, 3197–3200.
DOI Google Scholar
[170]

Lan, Q.; Zhang, Z. M.; Qin, C.; Wang, X. L.; Li, Y. G.; Tan, H. Q.; Wang, E. B. Highly dispersed polyoxometalate-doped porous Co3O4 water oxidation photocatalysts derived from POM@MOF crystalline materials. Chem.—Eur. J. 2016, 22, 15513–15520.
DOI Google Scholar
[171]

Ye, L.; Ying, Y. R.; Sun, D. R.; Qiao, J. L.; Huang, H. T. Ultrafine Mo2C nanoparticles embedded in an MOF derived N and P co-doped carbon matrix for an efficient electrocatalytic oxygen reduction reaction in zinc-air batteries. Nanoscale 2022, 14, 2065–2073.
DOI Google Scholar
[172]

Song, Y. T.; Peng, Y. W.; Yao, S.; Zhang, P.; Wang, Y. J.; Gu, J. M.; Lu, T. B.; Zhang, Z. M. Co-POM@MOF-derivatives with trace cobalt content for highly efficient oxygen reduction. Chin. Chem. Lett. 2022, 33, 1047–1050.
DOI Google Scholar
[173]

Steinlechner, C.; Junge, H. Renewable methane generation from carbon dioxide and sunlight. Angew. Chem., Int. Ed. 2018, 57, 44–45.
DOI Google Scholar
[174]

Inoue, T.; Fujishima, A.; Konishi, S.; Honda, K. Photoelectrocatalytic reduction of carbon dioxide in aqueous suspensions of semiconductor powders. Nature 1979, 277, 637–638.
DOI Google Scholar
[175]

Han, Q. X.; Qi, B.; Ren, W. M.; He, C.; Niu, J. Y.; Duan, C. Y. Polyoxometalate-based homochiral metal-organic frameworks for tandem asymmetric transformation of cyclic carbonates from olefins. Nat. Commun. 2015, 6, 10007.
DOI Google Scholar
[176]

Li, X. X.; Liu, J.; Zhang, L.; Dong, L. Z.; Xin, Z. F.; Li, S. L.; Huang-Fu, X. Q.; Huang, K.; Lan, Y. Q. Hydrophobic polyoxometalate-based metal-organic framework for efficient CO2 photoconversion. ACS Appl. Mater. Interfaces 2019, 11, 25790–25795.
DOI Google Scholar
[177]

Fang, Z.; Deng, Z.; Wan, X. Y.; Li, Z. Y.; Ma, X.; Hussain, S.; Ye, Z. Z.; Peng, X. S. Keggin-type polyoxometalates molecularly loaded in Zr-ferrocene metal organic framework nanosheets for solar-driven CO2 cycloaddition. Appl. Catal. B: Environ. 2021, 296, 120329.
DOI Google Scholar
[178]

Yan, A. X.; Yao, S.; Li, Y. G.; Zhang, Z. M.; Lu, Y.; Chen, W. L.; Wang, E. B. Incorporating polyoxometalates into a porous MOF greatly improves its selective adsorption of cationic dyes. Chem.—Eur. J. 2014, 20, 6927–6933.
DOI Google Scholar
[179]

Kaczmarek, A. M. Eu3+/Tb3+ and Dy3+ POM@MOFs and 2D coordination polymers based on pyridine-2,6-dicarboxylic acid for ratiometric optical temperature sensing. J. Mater. Chem. C 2018, 6, 5916–5925.
DOI Google Scholar
[180]

Zhou, E. L.; Qin, C.; Huang, P.; Wang, X. L.; Chen, W. C.; Shao, K. Z.; Su, Z. M. A stable polyoxometalate-pillared metal-organic framework for proton-conducting and colorimetric biosensing. Chem.—Eur. J. 2015, 21, 11894–11898.
DOI Google Scholar
[181]

Li, X.; Yang, X. Y.; Sha, J. Q.; Han, T.; Du, C. J.; Sun, Y. J.; Lan, Y. Q. POMOF/SWNT nanocomposites with prominent peroxidase-mimicking activity for L-cysteine “on-off switch” colorimetric biosensing. ACS Appl. Mater. Interfaces 2019, 11, 16896–16904.
DOI Google Scholar
[182]

Tong, Z. B.; Sha, J. Q.; Liu, D. Z.; Xu, M. Q. An unprecedented FeMo6@Ce-Uio-66 nanocomposite with cascade enzyme-mimic activity as colorimetric sensing platform. Chem.—Eur. J. 2022, 28, e202104213.
DOI Google Scholar
[183]

Wei, H.; Wang, E. Nanomaterials with enzyme-like characteristics (nanozymes): Next-generation artificial enzymes. Chem. Soc. Rev. 2013, 42, 6060–6093.
DOI Google Scholar
[184]

Wang, Z. K.; Bi, R.; Liu, J. D.; Wang, K. B.; Mao, F. F.; Wu, H.; Bu, Y. Q.; Song, N. H. Polyoxometalate-based Cu/Zn-MOFs with diverse stereo dimensions as anode materials in lithium ion batteries. Chem. Eng. J. 2021, 404, 127117.
DOI Google Scholar
[185]

Yang, X. Y.; Sha, J. Q.; Li, W. J.; Tan, Z. L.; Hou, L. R.; Jiang, J. Z. Ternary cross-vanadium tetra-capped POMOFs@PPy/RGO nanocomposites with hybrid battery-supercapacitor behavior for enhancing lithium battery storage. ACS Sustain. Chem. Eng. 2020, 8, 4667–4675.
DOI Google Scholar
[186]

Li, X.; Zhou, K. F.; Tong, Z. B.; Yang, X. Y.; Chen, C. Y.; Shang, X. H.; Sha, J. Q. Heightened integration of POM-based metal-organic frameworks with functionalized single-walled carbon nanotubes for superior energy storage. Chem.—Asian J. 2019, 14, 3424–3430.
DOI Google Scholar
[187]

Chai, D. F.; Gómez-García, C. J.; Li, B. N.; Pang, H. J.; Ma, H. Y.; Wang, X. M.; Tan, L. C. Polyoxometalate-based metal-organic frameworks for boosting electrochemical capacitor performance. Chem. Eng. J. 2019, 373, 587–597.
DOI Google Scholar
[188]

Wang, H. N.; Zhang, M.; Zhang, A. M.; Shen, F. C.; Wang, X. K.; Sun, S. N.; Chen, Y. J.; Lan, Y. Q. Polyoxometalate-based metal-organic frameworks with conductive polypyrrole for supercapacitors. ACS Appl. Mater. Interfaces 2018, 10, 32265–32270.
DOI Google Scholar
[189]

Chai, D. F.; Xin, J. J.; Li, B. N.; Pang, H. J.; Ma, H. Y.; Li, K. Q.; Xiao, B. X.; Wang, X. M.; Tan, L. C. Mo-based crystal POMOFs with a high electrochemical capacitor performance. Dalton Trans. 2019, 48, 13026–13033.
DOI Google Scholar
[190]

Yang, X. Y.; Li, W. J.; Tan, Z. L.; Sha, J. Q.; Tong, Z. B.; Zhang, Y.; Lan, Y. Q. Polyoxometalate-pillared metal-organic frameworks synthesized by surfactant-assisted strategy and incorporated with carbon nanotubes for energy storage. J. Mater. Chem. A 2020, 8, 25316–25322.
DOI Google Scholar
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Publication history

Received: 04 September 2022
Revised: 28 October 2022
Accepted: 01 November 2022
Published: 30 December 2022
Issue date: March 2023

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© The Author(s) 2023. Polyoxometalates published by Tsinghua University Press.

Acknowledgements

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 21871077, 22071042, 22171070, and 21771052), the Program for Innovation Teams in Science and Technology in Universities of Henan Province (No. 20IRTSTHN004) and the Doctoral Scientific Research Foundation of Henan Normal University (No. 20220016).

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