Polymorph Engineering of TiO2: Demonstrating How Absolute Reference Potentials Are Determined by Local Coordination

John Buckeridge, Keith T. Butler, C. Richard A. Catlow, Andrew J. Logsdail, David O. Scanlon, Stephen A. Shevlin, Scott M. Woodley, Alexey A. Sokol, Aron Walsh

Research output: Contribution to journalArticlepeer-review

79 Citations (Scopus)


We report that the valence and conduction band energies of TiO2 can be tuned over a 4 eV range by varying the local coordination environments of Ti and O. We examine the electronic structure of eight known polymorphs and align their ionization potential and electron affinity relative to an absolute energy reference, using an accurate multiscale quantum-chemical approach. For applications in photocatalysis, we identify the optimal combination of phases to enhance activity in the visible spectrum. The results provide a coherent explanation for a wide range of phenomena, including the performance of TiO2 as an anode material for Li-ion batteries, allow us to pinpoint hollandite TiO2 as a new candidate transparent conducting oxide, and serve as a guide to improving the efficiency of photo-electrochemical water splitting through polymorph engineering of TiO2.

Original languageEnglish
Pages (from-to)3844-3851
Number of pages8
JournalChemistry of Materials
Issue number11
Publication statusPublished - 2015 Jun 9

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry


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