CaltechAUTHORS
Published October 25, 2019 | Version Published
Journal Article Open

Modification of TiO₂ Nanoparticles with Organodiboron Molecules Inducing Stable Surface Ti³⁺ Complex

Creators

  • 1. ROR icon Peking University
  • 2. ROR icon Northwestern Polytechnical University
  • 3. ROR icon Beijing National Laboratory for Molecular Sciences
  • 4. ROR icon Beijing Technology and Business University
  • 5. ROR icon California State University, Northridge
  • 6. ROR icon California Institute of Technology
  • 7. ROR icon Shanxi University
  • 8. ROR icon Institute of Chemistry

Abstract

As one of the most promising semiconductor oxide materials, titanium dioxide (TiO₂) absorbs ultraviolet (UV) light but not visible light. To address this limitation, the introduction of Ti³⁺ defects represents a common strategy to render TiO₂ visible-light-responsive. Unfortunately, current hurdles in Ti³⁺ generation technologies impeded the widespread application of Ti³⁺ modified materials. Herein, we demonstrate a simple and mechanistically distinct approach to generating abundant surface-Ti³⁺ sites without leaving behind oxygen vacancy and sacrificing one-off electron donors. In particular, upon adsorption of organodiboron reagents onto TiO₂ nanoparticles, spontaneous electron injection from the dibron-bound O²⁻ site to adjacent Ti⁴⁺ site leads to an extremely stable blue surface Ti³⁺‒O⁻• complex. Notably, this defect generation protocol is also applicable to other semiconductor oxides including ZnO, SnO₂, Nb₂O₅ and In₂O₃. Furthermore, the as-prepared photoelectronic device using this strategy affords 10³ fold higher visible light response, and the fabricated perovskite solar cell shows an enhanced performance.

Additional Information

© 2019 The Author(s). Under a Creative Commons license - Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0). Received 25 June 2019, Revised 1 September 2019, Accepted 13 September 2019, Available online 18 September 2019. We thank J. C. Zhao for encouragement; H. J. Yang (Tsinghua University), G. Q. Liu (Peking University), S. L. Wang (Peking University), H. P. Zhou (Peking University) and L. Jiao (Tsinghua University) for insightful discussions; H. Fu (Peking University), H. J. Yang and X. Zhang (Peking University) for assistance with ^(11)B MAS NMR spectroscopy. A portion of EPR work was performed on the Steady High Magnetic Field Facilities, High Magnetic Field Laboratory of Chinese Academy of Sciences. The authors thank beamline BL08U1A and BL14W1 (Shanghai Synchrotron Radiation Facility) for providing the beam time. This research was supported by the National Natural Science Foundation of China (21772003, 91733301 and 91433203), the 973 Program of China (2015CB932203), ENN Group and BHP-PKU CCUS project. AUTHOR CONTRIBUTIONS: F. M. conceived the idea. Y. C., P. Z., Y. T., Z. L. and B.-W. D. performed experiments. Y. C., P. Z. and X. Z. conducted the DFT calculation. All authors analyzed data. Y. C., P. Z., Y. T., X. Z., Y. Y., S.-D. J., F. M. and W. M. wrote the manuscript. F. M. directed the whole project. The authors declare no competing interests.

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Additional details

Additional titles

Alternative title
Modification of TiO2 Nanoparticles with Organodiboron Molecules Inducing Stable Surface Ti3+ Complex

Identifiers

PMCID
PMC6833477
Eprint ID
98746
Resolver ID
CaltechAUTHORS:20190919-113941589

Funding

National Natural Science Foundation of China
21772003
National Natural Science Foundation of China
91733301
National Natural Science Foundation of China
91433203
National Basic Research Program of China
2015CB932203
BHP Billiton
Peking University

Dates

Created
2019-09-20
Created from EPrint's datestamp field
Updated
2022-02-17
Created from EPrint's last_modified field