A straightforward implementation of in situ solution electrochemical ¹³C NMR spectroscopy for studying reactions on commercial electrocatalysts: ethanol oxidation.

Identifying and quantifying electrocatalytic-reaction-generated solution species, be they reaction intermediates or products, are highly desirable in terms of understanding the associated reaction mechanisms. We report herein a straightforward implementation of in situ solution electrochemical (13)C NMR spectroscopy for the first time that enables in situ studies of reactions on commercial fuel-cell electrocatalysts (Pt and PtRu blacks). Using ethanol oxidation reaction (EOR) as a working example, we discovered that (1) the complete oxidation of ethanol to CO2 only took place dominantly at the very beginning of a potentiostatic chronoamperometric (CA) measurement and (2) the PtRu had a much higher activity in catalysing oxygen insertion reaction that leads to acetic acid.

Collisional 3He and 129Xe frequency shifts in Rb-noble-gas mixtures.

The Fermi-contact interaction that characterizes collisional spin exchange of a noble gas with an alkali-metal vapor also gives rise to NMR and EPR frequency shifts of the noble-gas nucleus and the alkali-metal atom, respectively. We have measured the enhancement factor κ0 that characterizes these shifts for Rb-129Xe to be 493±31, making use of the previously measured value of κ0 for Rb-3He. This result allows accurate 129Xe polarimetry with no need to reference a thermal-equilibrium NMR signal.