The voltammetry of Pt{111}, Pt{100}, Pt{110} and Pt{311} single crystal electrodes as a function of perchloric acid concentration (0.05-2.00 M) has been studied in order to test the assertion made in recent reports by Watanabe et al. that perchlorate anions specifically adsorb on polycrystalline platinum. Such an assertion would have significant ramifications for our understanding of electrocatalytic processes at platinum surfaces since perchlorate anions at low pH have classically been assumed not to specifically adsorb. For Pt{111}, it is found that OHad and electrochemical oxide states are both perturbed significantly as perchloric acid concentration is increased. We suggest that this is due to specific adsorption of perchlorate anions competing with OHad for adsorption sites. The hydrogen underpotential deposition (H UPD) region of Pt{111} however remains unchanged although evidence for perchlorate anion decomposition to chloride on Pt{111} is reported. In contrast, for Pt{100} no variation in the onset of electrochemical oxide formation is found nor any shift in the potential of the OHad state which normally results from the action of specifically adsorbing anions. This suggests that perchlorate anions are non-specifically adsorbed on this plane although strong changes in all H UPD states are observed as perchloric acid concentration is increased. This manifests itself as a redistribution of charge from the H UPD state situated at more positive potential to the one at more negative potential. For Pt{110} and Pt{311}, marginal changes in the onset of electrochemical oxide formation are recorded, associated with specific adsorption of perchlorate. Specific adsorption of perchlorate anions on Pt{111} is deleterious to electrocatalytic activity in relation to the oxygen reduction reaction (ORR) as measured using a rotating disc electrode (RDE) in a hanging meniscus configuration. This study supports previous work suggesting that a large component of the ORR activity on platinum is governed by simple site blocking by specifically adsorbed anions and/or electrosorbed oxide.
By flame-annealing and cooling a series of Pt n{110} × {111} and Pt n{110} × {100} single crystal electrodes in a CO ambient, new insights into the nature of the electrosorption processes associated with Pt{110} voltammetry in aqueous acidic media are elucidated. For Pt n{110} × {111} electrodes, a systematic change in the intensities of so-called hydrogen underpotential (Hupd) and oxide adsorption voltammetric peaks (for two dimensionally ordered (1 × 1) terraces and linear {111} × {111}step sites) point to a lack of surface reconstruction with all surfaces adopting a (1 × 1) configuration. This is in contrast to hydrogen cooled analogues which give rise to significant residual surface disorder, probably associated with the excess 50% of atoms remaining atop of the surface upon deconstruction of the {110} − (1 × 2) terrace phase. In contrast, Pt n{110} × {100} stepped electrodes, when cooled in gaseous CO following flame-annealing, show a marked tendency towards surface reconstruction, even at low step densities. Variations in potential of the Pt{110}-(1 × 1) Hupd electrosorption peaks as a function of specific ion adsorption strength and pH point to weak specific adsorption for both anions (including perchlorate and fluoride) and cations (including Na + and K +). CO charge-displacement measurements of the potential of zero total charge (PZTC) allow inferences to be made concerning the nature of the electrosorbed species in the hydrogen underpotential deposition (Hupd) region. Hence, a coherent interpretation of the complex voltammetric phenomena often displayed by platinum surfaces vicinal to the {110} plane is proposed.
Operando Raman spectroscopy is a well-established technique for monitoring chemical changes in active materials during electrochemical cycling of alkali-ion cells. To date, however, its application to the study of commercial electrodes under realistic operating conditions has been severely limited by cell design constraints. We present here an improved configuration for performing operando Raman spectroscopy on coated metal foil electrodes used in standard laboratory cell testing. Electrochemical modeling predicts much improved lithiation homogeneity compared to a previously used configuration; this observation is validated experimentally for a commercially-sourced graphite electrode. The new configuration delivers improved electrochemical performance at higher specific currents than was previously possible, ensuring that Raman measurements at a single location are representative of the entire electrode. Finally, the broad applicability of the configuration is demonstrated through a study of hard carbon sodium-ion negative electrodes over 50 cycles. These results provide a new configuration for performing reliable, validated operando Raman spectroscopy on commercial battery electrodes, as well as establishing a general methodological framework for the validation of operando spectroscopic techniques to ensure that their performance is relevant to the practical systems to which they are applied.
Uranyl complexes of aryl-substituted α-diimine ligands gbha (UO 2 -1a−f) and phen-BIAN (UO 2 -2a-f) [gbha (1) = glyoxal bis(2hydroxyanil); phen-BIAN (2) = N,N′-bis(iminophenol)acenaphthene; R = OMe (a), t-bu (b), H (c), Me (d), F (e), and naphthyl (f)] were designed, prepared, and characterized by X-ray diffraction, FT-IR, NMR, UV−vis, and electrochemical methods. These ligand frameworks contain a salen-type O− N−N−O binding pocket but are redox-noninnocent, leading to unusual metal complex behaviors. Here, we describe three solid-state structures of uranyl complexes UO 2 -1b, UO 2 -1c, and UO 2 -1f and observe manifestations of ligand noninnocence for the U(VI) complexes UO 2 -1b and UO 2 -1c. The impacts of accessible π-systems and ligand substitution on the axial uranium−oxo interactions were evaluated spectroscopically via the intraligand charge-transfer (ILCT) processes that dominate the absorption spectra of these complexes and through changes to the asymmetric (ν 3 ) OUO stretching frequency. This, in combination with electrochemical data, reveals the effects of the inclusion of the conjugated acenaphthene backbone and the importance of ligand electronic structure on uranyl's bonding interactions.
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