Defects and disorder: Probing the surface chemistry of heterogenite (CoOOH) by dissolution using hydroquinone and iminodiacetic acid

R. Lee Penn, Alan T. Stone, David R. Veblen

Research output: Contribution to journalArticle

66 Scopus citations

Abstract

High-resolution transmission electron microscopy (HRTEM) results show a strong crystal-chemical dependence on the mode of dissolution of synthetic heterogenite (CoOOH) particles via ligand-assisted dissolution using iminodiacetic acid (IDA) and reductive dissolution using hydroquinone (H2Q). Dissolution, using H2Q (10 μM to 2 mM) and IDA (10 μM to 2 mM), of synthesized heterogenite particles (37 mg/L) was examined in order to evaluate morphology evolution as a function of dissolution agent concentration. No evidence for redox reactions was observed in experiments using IDA, and no aqueous complexes of Co(II) or Co(III) with H2Q or benzoquinone, the oxidation product of H2Q, in experiments using H2Q were detected. As-synthesized heterogenite particles are micron-size hexagonal plates (aspect ratio, ∼1/30) constructed of crystallographically oriented ∼5 nm primary particles, or they are single ∼21 nm or ∼10 nm unattached heterogenite platelets (aspect ratio, ∼1/7 and ∼1/3, respectively). In experiments using the micron-sized hexagonal plates, two dominant modes of dissolution were observed: nonspecific dissolution that dissolved primary building blocks at all locations equally and pathway specific dissolution that occurred along boundaries of misorientation between primary building blocks. Both mechanisms occurred independent of the dissolution agent used. In comparison, TEM results show that dissolution of the unattached heterogenite particles occurs primarily at the {101} and {102̄}, or "edge," crystal faces and that no significant dissolution occurs at the (001), or "basal," crystal faces. This suggests that the reactive surface area is dominated by edge faces and further suggests that basal faces are essentially nonreactive under these conditions. Finally, dissolution by IDA produced two dissolved isomers, u-fac Co[IDA]2- and s-fac Co[IDA]2-. Experiments using identical solution conditions show that dissolution of the micron-sized plates favors the production of the u-fac isomer while dissolution of the 21 nm particles favors the production of the s-fac isomer.

Original languageEnglish (US)
Pages (from-to)4690-4697
Number of pages8
JournalJournal of Physical Chemistry B
Volume105
Issue number20
DOIs
StatePublished - May 24 2001

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