Abstract
Birnessite-like minerals are among the most common Mn oxides in surficial soils and sediments, and they mediate important environmental processes (e.g., biogeochemical cycles, heavy metal confinement) and have novel technological applications (e.g., water oxidation catalysis). Ca is the dominant interlayer cation in both biotic and abiotic birnessites, especially when they form in association with carbonates. The current study investigated the structures of a series of synthetic Ca-birnessite analogs prepared by cation-exchange with synthetic Na-birnessite at pH values from 2 to 7.5. The resulting Ca-exchanged birnessite phases were characterized using powder X‑ray diffraction and Rietveld refinement, Fourier transform infrared spectroscopy, Raman spectroscopy, X‑ray photoelectron spectroscopy, and scanning and transmission electron microscopy. All samples synthesized at pH values greater than 3 exhibited a similar triclinic structure with nearly identical unit-cell parameters. The samples exchanged at pH 2 and 3 yielded hexagonal structures, or mixtures of hexagonal and triclinic phases. Rietveld structure refinement and X‑ray photoelectron spectroscopy showed that exchange of Na by Ca triggered reduction of some Mn3+, generating interlayer Mn2+ and vacancies in the octahedral layers. The triclinic and hexagonal Ca-birnessite structures described in this study were distinct from Na- and H-birnessite, respectively. Therefore, modeling X‑ray absorption spectra of natural Ca-rich birnessites through mixing of Na- and H-birnessite end-members will not yield an accurate representation of the true structure.
Funding statement: We also acknowledge NSF EAR-1552211 and the Miller Faculty Fellowship (College of Earth and Mineral Sciences, PSU). This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. ESI was supported by U. S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES), Chemical Sciences, Geosciences, and Biosciences Division through its Geosciences program at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated by Battelle Memorial Institute under Contract No. DE-AC05-76RL01830 for the U.S. DOE. A portion of the research was performed using EMSL (grid.436923.9), a DOE Office of Science User Facility sponsored by the Office of Biological and Environmental Research.
Acknowledgments
This research was carried out at National Museum of Natural History, Department of Mineral Sciences, Smithsonian Institution. Scott D. Whittaker is kindly acknowledged for his technical support during the use of FEI Apreo scanning electron microscope at National Museum of Natural History, Smithsonian Institution. Si Athena Chen collected synchrotron X‑ray diffraction data at Beamline 13-BM_C at the Advanced Photon Source, Argonne National Laboratory. Ke Wang assisted with transmission electron microscopy in the Materials Characterization Laboratory, Penn State University. Four anonymous reviewers are kindly acknowledged for their thoughtful comments and suggestions that significantly improved the manuscript.
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