Gradually Fe-doped Co3O4 nanoparticles in 2-propanol and water oxidation catalysis with single laser pulse resolution.

Controlling the surface composition of colloidal nanoparticles is still a challenging yet mandatory prerequisite in catalytic studies to investigate composition-activity trends, active sites, and reaction mechanisms without superposition of particle size- or morphology-effects. Laser post-processing of colloidal nanoparticles has been employed previously to create defects in oxide nanoparticles, while the possibility of laser-based cation doping of colloidal nanoparticles without affecting their size, remains mostly unaccounted for. Consequently, at the example of doping iron into colloidal Co3O4 spinel nanoparticles, we developed a pulse-by-pulse laser cation doping method to provide catalyst series with gradual surface composition but maintained extrinsic properties such as phase, size, and surface area for catalytic studies. Laser pulse number-resolved doping series were prepared at laser intensity chosen to selectively heat the Co3O4-NPs to roughly 1000 K and enable cation diffusion of surface-adsorbed Fe3+ into the Co3O4 lattice while maintaining the spinel phase, particle size, and surface area. The combination of bulk-sensitive X-ray fluorescence (XRF) and surface-sensitive X-ray photoelectron spectroscopy (XPS) was used to confirm a surface enrichment of the Fe-dopant. XRD, Magnetometry, and Mössbauer spectroscopy revealed an increasing interaction between Fe and the antiferromagnetic Co3O4 with an increasing number of pulses, in line with a proposed laser-induced surface doping of colloidal Co3O4 with Fe. Using Fick’s second law the thermal diffusion-related doping depth was estimated to be roughly 2 nm after 4 laser pulses. At the example of gas-phase 2-propanol oxidation and liquid-phase oxygen evolution reaction, the activity of the laser-doped catalysts is in good agreement with previous observations on binary iron-cobalt oxides. The catalytic activity was found to linearly increases with the calculated doping depth in both reactions, while only catalysts processed with at least one laser pulse were catalytically stable, highlighting the presented method in providing comparable, active, and stable gradual catalyst doping series for future catalytic studies.