Nanoscale characterization of polyoxometalate catalysts by scanning tunneling microscopy

Polyoxometalates (POMs) are d{dollar}sp0{dollar} early transition metal oxide anion clusters that have found applications in acid and oxidation catalysis, electrode functionalization, and anti-retroviral therapy. Scanning tunneling microscopy (STM) is a powerful surface science technique that was used to determine the structural properties of self-assembled monolayers of POMs, and to probe the electronic properties of individual POM molecules.; In our studies, POMs were deposited from aqueous solutions onto graphite surfaces, and the STM operated in ambient conditions gave well-resolved images of the POM-derivatized surfaces, showing highly ordered, two-dimensional surface arrays (corrugations). The shape and periodicity of the corrugations were consistent with the molecular dimensions and structures of POMs as determined by X-ray diffraction. Different coadsorbed species were also imaged in air using STM; the species were distinguished based on differences in shapes and on electronic properties. These results are important steps toward real-space STM imaging of chemical reactions. Tunneling spectroscopy (TS) measurements (current-voltage, or I-V spectra) taken atop the corrugations and compared with the I-V spectra of bare graphite, confirmed that the STM imaged individual POM molecules in monolayer arrays on graphite. The characteristics of the POM monolayers, such as the effects of counter-cation substitution and anion-framework substitution on the ordered arrays, were also examined by STM. The ubiquity of the ordered array formation of these metal oxide clusters suggests that they can be utilized to create well-defined surfaces with more complex chemical functions than one typically encounters in studies of metal and oxide single crystal surfaces.; The POM corrugations exhibited localized electronic phenomena, referred to as negative differential resistance (NDR), at specific voltages in their I-V spectra. The NDR voltage in the I-V spectrum was dependent on the identity of the POM. Correlations were established between the NDR voltages and the reduction potentials of the POMs: more reducible POMs exhibited NDR behavior at smaller applied voltages in their I-V spectra. The spatial resolution of the TS measurements, plus the results of these experiments, suggests that this technique may be utilized to characterize the redox properties across a reactive surface on a site-by-site basis.