There is significant interest in the development of methods to create hybrid materials that transform capabilities, in particular for Earth-abundant metal oxides, such as TiO2, to give improved or new properties relevant to a broad spectrum of applications. Here we introduce an approach we refer to as ‘molecular cross-linking’, whereby a hybrid molecular boron oxide material is formed from polyhedral boron-cluster precursors of the type [B12(OH)12]2–. This new approach is enabled by the inherent robustness of the boron-cluster molecular building block, which is compatible with the harsh thermal and oxidizing conditions that are necessary for the synthesis of many metal oxides. In this work, using a battery of experimental techniques and materials simulation, we show how this material can be interfaced successfully with TiO2 and other metal oxides to give boron-rich hybrid materials with intriguing photophysical and electrochemical properties.
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Jaffe, R. L. et al. Energy Critical Elements: Securing Materials for Emerging Technologies (Materials Research Society/American Physical Society, Washington DC, 2011).
Reddy, M. V., Subba Rao, G. V. & Chowdari, B. V. R. Metal oxides and oxysalts as anode materials for Li ion batteries. Chem. Rev. 113, 5364–5457 (2013).
McFarland, E. W. & Metiu, H. Catalysis by doped oxides. Chem. Rev. 113, 4391–4427 (2013).
Chen, X. & Mao, S. S. Titanium dioxide nanomaterials: synthesis, properties, modifications, and applications. Chem. Rev. 107, 2891–2959 (2007).
Asahi, R., Morikawa, T., Irie, H. & Ohwaki, T. Nitrogen-doped titanium dioxide as visible-light-sensitive photocatalyst: designs, developments, and prospects. Chem. Rev. 114, 9824–9852 (2014).
Kapilashrami, M., Zhang, Y., Liu, Y.-S., Hagfeldt, A. & Guo, J. Probing the optical property and electronic structure of TiO2 nanomaterials for renewable energy applications. Chem. Rev. 114, 9662–9707 (2014).
Schneider, J. et al. Understanding TiO2 photocatalysis: mechanism and materials. Chem. Rev. 114, 9919–9986 (2014).
Fujishima, A. & Honda, K. Electrochemical photolysis of water at a semiconductor. Nature 238, 37–38 (1972).
Ma, Y. et al. Titanium dioxide-based nanomaterials for photocatalytic fuel generations. Chem. Rev. 114, 9987–10043 (2014).
Bai, Y., Mora-Seró, I., De Angelis, F., Bisquert, J. & Wang, P. Titanium dioxide nanomaterials for photovoltaic applications. Chem. Rev. 114, 10095–10130 (2014).
Khan, S. U. M., Al-Shahry, M. & Ingler, W. B. Jr Efficient photochemical water splitting by a chemically modified n-TiO2. Science 297, 2243–2245 (2002).
Chen, X., Liu, L., Yu, P. Y. & Mao, S. S. Increasing solar absorption for photocatalysis with black hydrogenated titanium dioxide nanocrystals. Science 331, 746–750 (2011).
Chen, X., Liu, L. & Huang, F. Black titanium dioxide (TiO2) nanomaterials. Chem. Soc. Rev. 44, 1861–1885 (2015).
Salzmann, I. & Heimel, G. Toward a comprehensive understanding of molecular doping organic semiconductors. J. Electron Spectrosc. Relat. Phenom. 204, 208–222 (2015).
Pitochelli, A. R. & Hawthorne, M. F. The isolation of the icosahedral B12H12 −2 ion. J. Am. Chem. Soc. 82, 3228–3229 (1960).
Spokoyny, A. M. New ligand platforms featuring boron-rich clusters as organomimetic substituents. Pure Appl. Chem. 85, 903–919 (2013).
Sivaev, I. B., Bregadze, V. I. & Sjöberg, S. Chemistry of closo-dodecaborate anion [B12H12]2–: a review. Collect. Czech. Chem. Commun. 67, 679–727 (2002).
Hawthorne, M. F. & Pushechnikov, A. Polyhedral borane derivatives: unique and versatile structural motifs. Pure Appl. Chem. 84, 2279–2288 (2012).
Dash, B. P., Satapathy, R., Maguire, J. A. & Hosmane, N. S. Polyhedral boron clusters in materials science. New J. Chem. 35, 1955–1972 (2011).
Hansen, B. R. S., Paskevicius, M., Li, H.-W., Akiba, E. & Jensen, T. R. Metal boranes: progress and applications. Coord. Chem. Rev. 323, 60–70 (2016).
Cheng, F. & Jäkle, F. Boron-containing polymers as versatile building blocks for functional nanostructured materials. Polym. Chem. 2, 2122–2132 (2011).
Núñez, R., Romero, I., Teixidor, F. & Viñas, C. Icosahedral boron clusters: a perfect tool for the enhancement of polymer features. Chem. Soc. Rev. 45, 5147–5173 (2016).
Alexandrova, A. N., Boldyrev, A. I., Zhai, H.-J. & Wang, L.-S. All-boron aromatic clusters as potential new inorganic and building blocks in chemistry. Coord. Chem. Rev. 250, 2811–2866 (2006).
Muetterties, E. L. Boron Hydride Chemistry (Academic, New York, NY, 1975).
Farha, O. K. et al. Synthesis of stable dodecaalkoxy derivatives of hypercloso-B12H12. J. Am. Chem. Soc. 127, 18243–18251 (2005).
Wixtrom, A. I. et al. Rapid synthesis of redox-active dodecaborane B12(OR)12 clusters under ambient conditions. Inorg. Chem. Front. 3, 711–717 (2016).
Messina, M. S. et al. Visible-light induced olefin activation using 3D aromatic boron-rich cluster photooxidants. J. Am. Chem. Soc. 138, 6952–6955 (2016).
Qian, E. A. et al. Atomically precise organomimetic cluster nanoparticles assembled via perfluoroaryl-thiol SNAr chemistry. Nat. Chem. 9, 333–340 (2017).
Pan, L. et al. Hierarchical nanostructured conducting polymer hydrogel with high electrochemical activity. Proc. Natl Acad. Sci. USA 109, 9287–9292 (2012).
To, J. W. F. et al. Ultrahigh surface area three-dimensional porous graphitic carbon from conjugated polymeric molecular framework. ACS Cent. Sci. 1, 68–76 (2015).
Mirabelli, M. G. L. & Sneddon, L. G. Synthesis of boron carbide via poly(vinylpentaborane) precursors. J. Am. Chem. Soc. 110, 3305–3307 (1988).
Su, K. & Sneddon, L. G. A polymer precursor route to metal borides. Chem. Mater. 5, 1659–1668 (1993).
Feng, N. et al. Boron environments in B-doped and (B,N)-codoped TiO2 photocatalysts: a combined solid-state NMR and theoretical calculation study. J. Phys. Chem. C 115, 2709–2719 (2011).
Barrow, N. S. et al. Towards homonuclear J-solid-state NMR correlation experiments for half-integer quadrupolar nuclei: experimental and simulated 11B MAS spin-echo dephasing and calculated 2 J BB coupling constants for lithium diborate. Phys. Chem. Chem. Phys. 13, 5778–5789 (2011).
Billinge, S. J. L. & Kanatzidis, M. G. Beyond crystallography: the study of disorder, nanocrystallinity and crystallographically challenged materials with pair distribution functions. Chem. Commun. 0, 749–760 (2004).
Lee, M. W., Farha, O. K., Hawthorne, M. F. & Hansch, C. H. Alkoxy derivatives of dodecaborate: discrete nanomolecular ions with tunable pseudometallic properties. Angew. Chem. Int. Ed. 46, 3018–3022 (2007).
Van, N. et al. Oxidative perhydroxylation of [closo-B12H12]2– to the stable inorganic cluster redox system [B12(OH)12]2–/•–: experiment and theory. Chem. Eur. J. 16, 11242–11245 (2010).
Li, Y. et al. An oxygen reduction electrocatalyst based on carbon nanotube-graphene complexes. Nat. Nanotech. 7, 394–400 (2012).
Guo, Y.-G., Hu, Y.-S., Sigle, W. & Maier, J. Superior electrode performance of nanostructured mesoporous TiO2 (anatase) through efficient hierarchical mixed conducting networks. Adv. Mater. 19, 2087–2091 (2007).
Jiang, C., Hosono, E. & Zhou, H. Nanomaterials for lithium ion batteries. Nano Today 1, 28–33 November, (2006).
Gomes, A., Fernandes, E. & Lima, J. L. F. C. Fluorescence probes used for detection of reactive oxygen species. J. Biochem. Biophys. Methods 65, 45–80 (2005).
Yin, Q. et al. A fast soluble carbon-free molecular water oxidation catalyst based on abundant metals. Science 328, 342–345 (2010).
Yan, H. et al. Hybrid metal–organic chalcogenide nanowires with electrically conductive inorganic core through diamondoid-directed assembly. Nat. Mater. 16, 349–355 (2017).
Bag, S., Trikalitis, P. N., Chupas, P. J., Armatas, G. S. & Kanatzidis, M. G. Porous semiconducting gels and aerogels from chalcogenide clusters. Science 317, 490–493 (2007).
Song, J. et al. A multiunit catalyst with synergistic stability and reactivity: a polyoxometalate–metal organic framework for aerobic decontamination. J. Am. Chem. Soc. 133, 16839–16846 (2011).
Yaghi, O. M., Li, G. & Li, H. Selective binding and removal of guests in a microporous metal–organic framework. Nature 378, 703–706 (1995).
Bachman, J. E., Smith, Z. P., Li, T., Xu, T. & Long, J. R. Enhanced ethylene separation and plasticization resistance in polymer membranes incorporating metal-organic framework nanocrystals. Nat. Mater. 15, 845–849 (2016).
Wang, C., Xie, Z., deKrafft, K. E. & Lin, W. Doping metal–organic frameworks for water oxidation, carbon dioxide reduction and organic photocatalysis. J. Am. Chem. Soc. 133, 13445–13454 (2011).
Goellner, J. F., Gates, B. C., Vayssilov, G. N. & Rösch, N. Structure and bonding of a site-isolated transition metal complex: rhodium dicarbonyl in highly dealuminated zeolite Y. J. Am. Chem. Soc. 122, 8056–8066 (2000).
Pryor, A. Jr. et al. GENFIRE: a generalized Fourier iterative reconstruction algorithm for high-resolution 3D imaging. Sci. Rep. 7, 10409 (2017).
Yang, Y. et al. Deciphering chemical order/disorder and material properties at the single-atom level. Nature 542, 75–79 (2017).
Fung, B. M., Khitrin, A. K. & Ermolav, K. An improved broadband decoupling sequence for liquid crystals and solids. J. Magn. Reson. 142, 97–101 (2000).
Yesinowski, J. P. Finding the true-spin-lattice relaxation time for half-integral nuclei with non-zero quadrupolar couplings. J. Mag. Reson. 252, 135–144 (2015).
Johnston, D. C. Stretched exponential relaxation arising from a continuous sum of exponential decays. Phys. Rev. B. 74, 184430 (2006).
Brouwer, D. H., Kristiansen, P. E., Fyfe, C. A. & Levitt, M. H. Symmetry-based 29Si dipolar recoupling magic angle spinning NMR spectroscopy: a new method for investigating three-dimensional structures of zeolite frameworks. J. Am. Chem. Soc. 127, 542–543 (2005).
Nicholson, R. S. Theory and application of cyclic voltammetry for measurement of electrode reaction kinetics. Anal. Chem. 37, 1351–1355 (1965).
Moldenhauer, J., Meier, M. & Paul, D. W. Rapid and direct determination of diffusion coefficients using microelectrode arrays. J. Electrochem. Soc. 163, H672–H678 (2016).
Konopka, S. J. & McDuffie, B. Diffusion coefficients of ferri-and ferrocyanide ions in aqueous media, using twin-electrode thin-layer electrochemistry. Anal. Chem. 42, 1741–1746 (1970).
A.M.S. thanks the University of California, Los Angeles (UCLA), Department of Chemistry and Biochemistry for start-up funds, 3M for a Non-Tenured Faculty Award and the Alfred P. Sloan Foundation for a research fellowship in chemistry. The authors thank the MRI program of the National Science Foundation (NSF grant no. 1532232 and no.1625776) for sponsoring the acquisition of SSNMR equipment and SQUID, respectively, at UCLA. Z.J.B. was supported by a grant from the BASF Corporation, and the solid-state MAS NMR measurements at the University of California, Santa Barbara (UCSB), made use of the shared facilities of the UCSB MRSEC (NSF DMR 1720256), a member of the Materials Research Facilities Network (www.mrfn.org). E.C.W. and J.T.M. were supported by the National Science Foundation Energy Research Center for Innovative and Strategic Transformations of Alkane Resources (CISTAR) under the cooperative agreement no. EEC-1647722. J.I.Z. thanks the Student and Research Support Fund for financial support. The computational modelling benefited from access to the Extreme Science and Engineering Discovery Environment, which is supported by NSF Grant ACI-1053575. R.R.L. and M.D. were supported by the US Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Biosciences and Geosciences under Contract DE-AC02-06CH11357. This research used resources of the APS, a US DOE Office of Basic Energy Sciences and Office of Science User Facility, operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. MRCAT operations, beamline 10-BM, are supported by the DOE and the MRCAT member institutions.
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A correction to this article is available online at https://doi.org/10.1038/s41563-018-0054-0.
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Jung, D., Saleh, L.M.A., Berkson, Z.J. et al. A molecular cross-linking approach for hybrid metal oxides. Nature Mater 17, 341–348 (2018). https://doi.org/10.1038/s41563-018-0021-9
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