Determination of the valence band edge of Fe oxide nanoparticles dispersed in aqueous solution through resonant photoelectron spectroscopy from a liquid microjet.

We use X-ray photoemission and a near ambient pressure with a liquid microjet setup to investigate the electronic structure of FeOOH nanoparticles dispersed in aqueous solution. In particular, we show that by using X-ray resonant photoemission in dilute solutions, we can overcome the limits of conventional photoemission such as low nanoparticle-to-solvent signal ratio, and local nanoparticle charging and measure the valence band structure of FeOOH nanoparticles in aqueous solution with chemical specificity. The resonant photoemission signal across the Fe 2p absorption edge is measured for 2 wt% aqueous solutions of FeOOH nanoparticles (NPs) and the valence band maximum (VBM) of the hydrated FeOOH nanoparticles is determined. We compare the obtained VBM value in aqueous solution to that of FeOOH NPs in the dry phase. We show that the valence band edge position of NPs in the liquid phase can be accurately predicted from the values obtained in the dry phase provided that a simple potential shift due to solution chemistry is applied. Our results demonstrate the suitability of resonant photoemission in measuring the electronic structure of strongly diluted nanosystems where the conventional non-resonant photoemission technique fails.