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A major concern of electrocatalysis research is to assess the structural and chemical changes that a catalyst may itself undergo in the course of the catalyzed process. These changes can influence not only the activity of the studied catalyst but also its selectivity toward the formation of a certain product. An illustrative example is the electroreduction of carbon dioxide on tin oxide nanoparticles, where under the operating conditions of the electrolysis (that is, at cathodic potentials), the catalyst undergoes structural changes which, in an extreme case, involve its reduction to metallic tin. This results in a decreased Faradaic efficiency (FE) for the production of formate (HCOO–) that is otherwise the main product of CO2 reduction on SnO x surfaces. In this study, we utilized potential- and time-dependent in operando Raman spectroscopy in order to monitor the oxidation state changes of SnO2 that accompany CO2 reduction. Investigations were carried out at different alkaline pH levels, and a strong correlation between the oxidation state of the surface and the FE of HCOO– formation was found. At moderately cathodic potentials, SnO2 exhibits a high FE for the production of formate, while at very negative potentials the oxide is reduced to metallic Sn, and the efficiency of formate production is significantly decreased. Interestingly, the highest FE of formate production is measured at potentials where SnO2 is thermodynamically unstable; however, its reduction is kinetically hindered.

The electrochemical reduction of CO 2 has been extensively studied over the past decades. Nevertheless, this topic has been tackled so far only by using a very fundamental approach and mostly by trying to improve kinetics and selectivities toward specific products in half-cell configurations and liquid-based electrolytes. The main drawback of this approach is that, due to the low solubility of CO 2 in water, the maximum CO 2 reduction current which could be drawn falls in the range of 0.01-0.02 A cm -2 . This is at least an order of magnitude lower current density than the requirement to make CO 2 -electrolysis a technically and economically feasible option for transformation of CO 2 into chemical feedstock or fuel thereby closing the CO 2 cycle. This work attempts to give a short overview on the status of electrochemical CO 2 reduction with respect to challenges at the electrolysis cell as well as at the catalyst level. We will critically discuss possible pathways to increase both operating current density and conversion efficiency in order to close the gap with established energy conversion technologies.

In this paper we combine two operando methods, Raman spectroscopy and X-ray absorption spectroscopy (XAS), in order to probe graphene-oxide supported tin IV oxide nanoparticles (SnO 2 NPs@rGO) as they are being used to catalyse CO 2 electroreduction. To achieve high reaction rates it is necessary to apply sufficiently cathodic electrode potentials. Under such conditions, however, not only CO 2 is reduced electrochemically, but also the catalyst particles may be transformed from the initial Sn IV state to Sn II or, in an extreme case, to metallic Sn. While Sn II species still favour CO 2 electroreduction, yielding formate as a primary product, on metallic Sn CO 2 reduction is disfavoured with respect to the competing hydrogen evolution reaction (HER). We show that operando XAS, a robust technique yielding information averaged over a large surface area and a relatively large thickness of the catalyst layer, is a very expedient method able to detect the reduction of SnO 2 NPs@rGO to metallic Sn. XAS can thus be used to establish an optimum potential for the electroreduction in practical electrolysing cells. It takes, however, a complementary method offered by operando Raman spectroscopy, having greater sensitivity at the catalyst/electrolyte solution interface, to probe reduction intermediates such as the Sn II state, which remain undetectable for ex situ methods. As it is shown in the paper, Raman spectroscopy may also find further use when investigating the recovery of catalyst particles following exposure to extreme reducing conditions.

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The ability of Geobacter species to transfer electrons outside the cell enables them to play an important role in a number of biogeochemical and bioenergy processes. Gene deletion studies have implicated periplasmic and outer-surface c-type cytochromes in this extracellular electron transfer. However, even when as many as five c-type cytochrome genes have been deleted, some capacity for extracellular electron transfer remains. In order to evaluate the role of c-type cytochromes in extracellular electron transfer, Geobacter sulfurreducens was grown in a low-iron medium that included the iron chelator (2,2'-bipyridine) to further sequester iron. Haem-staining revealed that the cytochrome content of cells grown in this manner was 15-fold lower than in cells exposed to a standard iron-containing medium. The low cytochrome abundance was confirmed by in situ nanoparticle-enhanced Raman spectroscopy (NERS). The cytochrome-depleted cells reduced fumarate to succinate as well as the cytochrome-replete cells do, but were unable to reduce Fe(III) citrate or to exchange electrons with a graphite electrode. These results demonstrate that c-type cytochromes are essential for extracellular electron transfer by G. sulfurreducens. The strategy for growing cytochrome-depleted G. sulfurreducens will also greatly aid future physiological studies of Geobacter species and other microorganisms capable of extracellular electron transfer.

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