TiO2(110)-(1 × 1) supported Cu particles: An FT-RAIRS investigation

The morphology of TiO2(110)-(1 × 1) supported Cu particles has been investigated by Fourier Transform Reflection Absorption Infrared Spectroscopy (FT-RAIRS), employing adsorbed CO as a probe molecule sensitive to local surface structure. For Cu coverage (deposited at 300 K) less than 2.85 MLE nucleated Cu particles in the range 2 nm-4 nm are formed, as indicated by a final state shift in the core level Cu(2p3/2) binding energy and by the existence of only transmission bands in the FT-RAIRS spectra for adsorbed CO. νS(CO) indicates that these small particles expose sites similar to those of the stepped Cu surfaces Cu(211), Cu(311), and Cu(755). At Cu coverages in the range of 6 MLE and above, corresponding to particle sizes above 4.6 nm, νS(CO) indicates the predominance of (110), (100) and (111) adsorption sites. Annealing the Cu layers to 650 K results in the slight growth of the particle sizes, and transformation of the CO adsorption sites corresponding to the close packed facets. The transformation of the local dielectric from that of titania to that dominated by the Cu particle is shown to take place between 3.7 and 4.2 nm, and this change is also to a smaller extent sensitive to the dispersion of the particles.