Stable Molecular Surface Modification of Nanostructured, Mesoporous Metal Oxide Photoanodes by Silane and Click Chemistry

Lei Wu, Michael Eberhart, Bing Shan, Animesh Nayak, M. Kyle Brennaman, Alexander J.M. Miller, Jing Shao, Thomas J. Meyer

Research output: Contribution to journalArticlepeer-review

18 Scopus citations


Binding functional molecules to nanostructured mesoporous metal oxide surfaces provides a way to derivatize metal oxide semiconductors for applications in dye-sensitized photoelectrosynthesis cells (DSPECs). The commonly used anchoring groups, phosphonates and carboxylates, are unstable as surface links to oxide surfaces at neutral and high pH, leading to rapid desorption of appended molecules. A synthetically versatile molecular attachment strategy based on initial surface modification with a silyl azide followed by click chemistry is described here. It has been used for the stable installation of surface-bound metal complexes. The resulting surfaces are highly stabilized toward complex loss with excellent thermal, photochemical, and electrochemical stabilities. The procedure involves binding 3-azidopropyltrimethoxysilane (APTMS) to nanostructured mesoporous TiO 2 or tin-doped indium oxide (ITO) electrodes by silane attachment followed by azide-terminated, Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reactions with an alkyne-derivatized ruthenium(II) polypyridyl complex. The chromophore-modified electrodes display enhanced photochemical and electrochemical stabilities compared to phosphonate surface binding with extended photoelectrochemical oxidation of hydroquinone for more than 6 h with no significant decay.

Original languageEnglish (US)
Pages (from-to)4560-4567
Number of pages8
JournalACS Applied Materials and Interfaces
Issue number4
StatePublished - Jan 30 2019
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • General Materials Science


  • DSPECs
  • Ru(II) polypyridyl complexes
  • click chemistry
  • dye-sensitized
  • electrostability
  • photoanode
  • photostability
  • silane chemistry
  • stability


Dive into the research topics of 'Stable Molecular Surface Modification of Nanostructured, Mesoporous Metal Oxide Photoanodes by Silane and Click Chemistry'. Together they form a unique fingerprint.

Cite this