Surface modification of TiO2 with copper clusters for band gap narrowing

Thumbnail Image
4462.pdf(1.26 MB)
Accepted version
Sharma, Preetam K.
Cortes, Maria Ana L. R. M.
Hamilton, Jeremy W. J.
Han, Yisong
Byrne, J. Anthony
Nolan, Michael
Journal Title
Journal ISSN
Volume Title
Research Projects
Organizational Units
Journal Issue
Surface modification of photocatalytic materials to give better activity, and potentially extending the response into the visible spectrum, is an area of active research. In this work, DFT modelling suggests that surface modification of rutile and anatase TiO2 with partially oxidised copper clusters can induce a red shift in the photo-action spectrum. Copper clusters were synthesised and characterised separately before TiO2 nanoparticle surface modification. Characterisation of copper clusters and photocatalysts modified with copper clusters showed that ex-situ synthesis can control the size of surface clusters. Sub-nanometre clusters of copper maintained their size and morphology upon attachment to the photocatalyst surface. The copper clusters we determined to be a mixture of Cu(0) and Cu(I), and no significant change in the oxidation state was observed following surface modification or following photoelectrochemical measurements. Experimental measurements including UV–vis spectroscopy and valence band XPS showed a small red shift the band gap correlating to the DFT predictions. Photoelectrochemical characterisation showed an enhancement in the UV photocurrent response and a small red shift in the effective band gap for the surface modified TiO2.
TiO2 , Copper clusters , Surface modification , Band gap engineering , DFT modelling , X-ray photoelectron spectroscopy , Photoelectrochemical water splitting
Sharma, P. K., Cortes, M. A. L. R. M., Hamilton, J. W. J., Han, Y., Byrne, J. A. and Nolan, M. (2017) 'Surface modification of TiO2 with copper clusters for band gap narrowing', Catalysis Today, 321-322, pp. 9-17. doi: 1016/j.cattod.2017.12.002