In any artificial photosynthetic system, the oxidation of water to molecular oxygen provides the electrons needed for the reduction of protons or carbon dioxide to a fuel. Understanding how this four-electron reaction works in detail is important for the development of improved robust catalysts made of Earth-abundant materials, like first-row transition-metal oxides. Here, using time-resolved Fourier-transform infrared spectroscopy and under reaction conditions, we identify intermediates of water oxidation catalysed by an abundant metal-oxide catalyst, cobalt oxide (Co3O4). One intermediate is a surface superoxide (three-electron oxidation intermediate absorbing at 1,013 cm(-1)), whereas a second observed intermediate is attributed to an oxo Co(IV) site (one-electron oxidation intermediate absorbing at 840 cm(-1)). The temporal behaviour of the intermediates reveals that they belong to different catalytic sites. Knowledge of the structure and kinetics of surface intermediates will enable the design of improved metal-oxide materials for more efficient water oxidation catalysis.

Light, inexpensive, effective: Nanostructured Co3O4 clusters (see picture) in mesoporous silica are the first example of a nanometer‐sized multielectron catalyst made of a first‐row transition‐metal oxide that evolves oxygen from water efficiently. The nanorod bundle structure of the catalyst results in a very large surface area, an important factor contributing to the high turnover frequency.

The vibrational spectra of platinum nanoparticles (2.4-9 nm) capped with poly(N-vinylpyrrolidone) (PVP) were investigated by deep UV-Raman and FTIR spectroscopy and compared with those of pure PVP. Raman spectra of PVP/Pt show selective enhancement of C=O, C-N, and CH2 vibrational modes attributed to the pyrrolidone ring. Selective enhancement of ring vibrations is attributed both to the resonance Raman effect and SERS chemical enhancement. A red shift of the PVP carbonyl frequency on the order of 60 cm-1 indicates the formation of strong >C=O-Pt bonds. It is concluded that PVP adheres to the nanoparticles through a charge-transfer interaction between the pyrrolidone rings and surface Pt atoms. Heating the Pt nanoparticles under reducing conditions initiates the decomposition of the capping agent, PVP, at a temperature 100 degrees C below that of pure PVP. Under oxidizing conditions, both PVP/Pt and PVP degrade to form amorphous carbon.