9966
Views
554
Downloads
12
Crossref
N/A
WoS
N/A
Scopus
N/A
CSCD
In this work, two heterometallic clusters, namely TiIV4MoV4MoVI2O16(OCH3)16 (1) and TiIV4MoV4O10(OC2H5)14 (C6H5COO)2 (2) are successfully constructed to improve the solar absorption and performance of titanium oxo clusters (TOCs). The 1 and 2 structures are determined well by single-crystal X-ray diffraction analysis and found to feature the common presence of Mo–Mo interactions. The solid-state UV–vis absorption studies indicate that these structures exhibit enhanced visible-light absorption and significantly reduced optical band gaps, which should be dominantly attributed to the introduction of electron-rich Mo–Mo pairs as heterometals. This work demonstrates an effective strategy of regulating the light absorption behaviors of TOCs by importing electron-rich heterometals.
In this work, two heterometallic clusters, namely TiIV4MoV4MoVI2O16(OCH3)16 (1) and TiIV4MoV4O10(OC2H5)14 (C6H5COO)2 (2) are successfully constructed to improve the solar absorption and performance of titanium oxo clusters (TOCs). The 1 and 2 structures are determined well by single-crystal X-ray diffraction analysis and found to feature the common presence of Mo–Mo interactions. The solid-state UV–vis absorption studies indicate that these structures exhibit enhanced visible-light absorption and significantly reduced optical band gaps, which should be dominantly attributed to the introduction of electron-rich Mo–Mo pairs as heterometals. This work demonstrates an effective strategy of regulating the light absorption behaviors of TOCs by importing electron-rich heterometals.
Chu, S.; Majumdar, A. Opportunities and challenges for a sustainable energy future. Nature 2012, 488, 294–303.
Kment, S.; Riboni, F.; Pausova, S.; Wang, L.; Wang, L. Y.; Han, H.; Hubicka, Z.; Krysa, J.; Schmuki, P.; Zboril, R. Photoanodes based on TiO2 and α-Fe2O3 for solar water splitting-superior role of 1D nanoarchitectures and of combined heterostructures. Chem. Soc. Rev. 2017, 46, 3716–3769.
Chen, X. B.; Liu, L.; Huang, F. Q. Black titanium dioxide (TiO2) nanomaterials. Chem. Soc. Rev. 2015, 44, 1861–1885.
Chen, X. B.; Liu, L.; Yu, P. Y.; Mao, S. S. Increasing solar absorption for photocatalysis with black hydrogenated titanium dioxide nanocrystals. Science 2011, 331, 746–750.
Fang, W. H.; Zhang, L.; Zhang, J. Synthetic strategies, diverse structures and tuneable properties of polyoxo-titanium clusters. Chem. Soc. Rev. 2018, 47, 404–421.
Rozes, L.; Sanchez, C. Titanium oxo-clusters: Precursors for a Lego-like construction of nanostructured hybrid materials. Chem. Soc. Rev. 2011, 40, 1006–1030.
Liu, Y. J.; Fang, W. H.; Zhang, L.; Zhang, J. Recent advances in heterometallic polyoxotitanium clusters. Coord. Chem. Rev. 2020, 404, 213099.
Gao, M. Y.; Wang, F.; Gu, Z. G.; Zhang, D. X.; Zhang, L.; Zhang, J. Fullerene-like polyoxotitanium cage with high solution stability. J. Am. Chem. Soc. 2016, 138, 2556–2559.
Fan, X.; Wang, J. H.; Wu, K. F.; Zhang, L.; Zhang, J. Isomerism in titanium-Oxo clusters: Molecular anatase model with atomic structure and improved photocatalytic activity. Angew. Chem., Int. Ed. 2019, 58, 1320–1323.
Zheng, H.; Du, M. H.; Lin, S. C.; Tang, Z. C.; Kong, X. J.; Long, L. S.; Zheng, L. S. Assembly of a wheel-like Eu24Ti8 cluster under the guidance of high-resolution electrospray ionization mass spectrometry. Angew. Chem., Int. Ed. 2018, 57, 10976–10979.
Wang, C.; Liu, C.; Li, L. J.; Sun, Z. M. Synthesis, crystal structures, and photochemical properties of a family of heterometallic titanium Oxo clusters. Inorg. Chem. 2019, 58, 6312–6319.
Timco, G. A.; Fernandez, A.; Kostopoulos, A. K.; Muryn, C. A.; Pritchard, R. G.; Strashnov, I.; Vitorica-Yrezebal, I. J.; Whitehead, G. F. S.; Winpenny, R. E. P. An extensive family of heterometallic titanium(IV)-metal(III) rings with structure control through templates. Angew. Chem., Int. Ed. 2017, 56, 13629–13632.
Fan, X.; Chen, S.; Zhang, L.; Zhang, J. Protection of Ag clusters by metal-Oxo modules. Chem.—Eur. J. 2021, 27, 15563–15570.
Zhou, S. Y.; Li, C. P.; Fu, H.; Cao, J.; Zhang, J.; Zhang, L. Lead-doped titanium-oxo clusters as molecular models of perovskite-type PbTiO3 and electron-transport material in solar cells. Chem.—Eur. J. 2020, 26, 6894–6898.
Yang, L.; Shu, X. P.; Fu, M. Y.; Wang, H. Y.; Zhu, Q. Y.; Dai, J. Molybdenum-titanium oxo-cluster, an efficient electrochemical catalyst for the facile preparation of black titanium dioxide film. Dalton Trans. 2020, 49, 10516–10522.
Uchiyama, H.; Puthusseri, D.; Grins, J.; Gribble, D.; Seisenbaeva, G. A.; Pol, V. G.; Kessler, V. G. Single-source alkoxide precursor approach to titanium molybdate, TiMoO5, and its structure, electrochemical properties, and potential as an anode material for alkali metal ion batteries. Inorg. Chem. 2021, 60, 3593–3603.
Eslava, S.; Goodwill, B. P. R.; McPartlin, M.; Wright, D. S. Extending the family of titanium heterometallic-oxo-alkoxy cages. Inorg. Chem. 2011, 50, 5655–5662.
du Peloux, C.; Mialane, P.; Dolbecq, A.; Marrot, J.; Sécheresse, F. MoV/pyrophosphate polyoxometalate: An inorganic cryptate. Angew. Chem., Int. Ed. 2002, 41, 2808–2810.
du Peloux, C.; Dolbecq, A.; Mialane, P.; Marrot, J.; Rivière, E.; Sécheresse, F. A new family of layered molybdenum(V) cobalto-phosphates built up of [H14(Mo16O32)Co16(PO4)24(H2O)20]10– wheels. Angew. Chem., Int. Ed. 2001, 40, 2455–2457.
Ren, C. M.; Lu, Z. H.; Luo, B. L.; Yi, X. F.; Lin, L. F.; Xu, L. Deeply reduced empty Keggin clusters [MoIVxMVI12−xO40−xpyx] (x = 3, 6; M = Mo, W; py = pyridine): Synthesis, structures, and Lewis field catalysis. Inorg. Chem. Front. 2021, 8, 5178–5185.
Gao, M. Y.; Sun, Y. Y.; Wang, F.; Zhang, J.; Zhang, L. Synthesis and structure of a series of Ti6-oxo clusters functionalized by in situ esterified dicarboxylate ligands. Chin. J. Chem. 2021, 39, 1259–1264.
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.
Nohra, B.; El Moll, H.; Rodriguez Albelo, L. M.; Mialane, P.; Marrot, J.; Mellot-Draznieks, C.; O'Keeffe, M.; Ngo Biboum, R.; 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.
Manos, M. J.; Woollins, J. D.; Slawin, A. M. Z.; Kabanos, T. A. Polyoxomolybdenum(V) sulfite complexes: Synthesis, structural, and physical studies. Angew. Chem., Int. Ed. 2002, 41, 2801–2805.
Liu, J. X.; Gao, M. Y.; Fang, W. H.; Zhang, L.; Zhang, J. Bandgap engineering of titanium-oxo clusters: Labile surface sites used for ligand substitution and metal incorporation. Angew. Chem., Int. Ed. 2016, 55, 5160–5165.
Research reported in this publication was supported by the National Natural Science Foundation of China (Nos. 21901241 and 21922111) and the Natural Science Foundation of Fujian Province (No. 2020J01117).
The articles published in this open access journal are distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits use, distribution and reproduction in any medium, provided the original work is properly cited.