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Role of cyclic voltammetry in characterizing solids: Natural and synthetic manganese oxide octahedral molecular sieves

Journal Article · · Chemistry of Materials; (United States)
DOI:https://doi.org/10.1021/cm00034a006· OSTI ID:5222911
; ; ;  [1];  [2]
  1. Univ. of Connecticut, Storrs, CN (United States)
  2. Texaco Inc., Beacon, NY (United States)
Octahedral molecular sieves (OMS) having the todorokite (OMS-1) and hollandite (OMS-2) structures were used to modify carbon paste electrodes, and their cyclic voltammograms were recorded. The presence of Mn[sup 2+] in OMS-1 makes it electroactive; OMS-2 is not electroactive. Synthetic and natural todorokites showed very similar cyclic volammetric responses despite the difference in tunnel counter cations. Natural todorokites may contain different tunnel counter cations such as Mg[sup 2+], Ba[sup 2+], and K[sup +], while synthetic todorokite was prepared with Mg[sup 2+] as the counter cation in the tunnels. The different tunnel counter cations such as Mg[sup 2+], Ba[sup 2+], and K[sup +] do not influence the electrochemistry of either synthetic or natural todorokites. This observation suggests that the observed electroactivity of synthetic and natural todorokite may be due to framework Mn[sup 2+]. Todorokite synthesized in the presence of Cu[sup 2+] (Cu-OMS-1) was also used to modify carbon paste electrodes. Results indicate that Cu[sup 2+] in the Cu-OMS-1 is electroactive and mobile, but cannot be completely removed, suggesting that Cu[sup 2+] is located in the tunnels of Cu-OMS-1. OMS-1 modified carbon paste electrodes show an enhancement in the signal for Cu[sup 2+] ion in solution over that of unmodified electrodes. Cu[sup 2+] can exchange reversibly into and out of the tunnels of OMS-1 during cyclic volammetric experiments. 32 refs., 14 figs., 3 tabs.
OSTI ID:
5222911
Journal Information:
Chemistry of Materials; (United States), Journal Name: Chemistry of Materials; (United States) Vol. 5:10; ISSN CMATEX; ISSN 0897-4756
Country of Publication:
United States
Language:
English