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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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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