Solid-State Hydroxide Ion Conductivity in Silver(I) Oxide, Ag<sub>2</sub>O
Silver(I) oxide, Ag2O, precipitated as microcrystals by combining aqueous silver(I) nitrate and KOH solutions, was found to be a solid-state hydroxide ion conductor with ionic conductivity on the order of 10–3 S/cm. The proton chemical shifts at 4.87 and −7.35 ppm measured by solid-state 1H NMR experiments are attributed to water molecules and in-lattice OH– coordinated to silver, respectively. The lack of spinning sidebands around the 4.87 ppm peak indicates rapid reorientation on the NMR time scale, suggesting that the water molecules are adsorbed to the surface of the Ag2O crystals. Pulsed field gradient measurements gave similar diffusion coefficients (2 × 10–7 cm2/s at 298 K) for all three proton environments, indicating chemical exchange between sites on the millisecond time scale. The activation energy for OH– diffusion measured by NMR (0.18 eV) was comparable to that obtained by conductivity measurements and density functional theory (DFT) electronic structure calculations. The calculated Pourbaix diagram of Ag2O is consistent with the slightly lower sample density observed in He pycnometry and thermogravimetric measurements.
Authors
- Woo Hyun Jung (ORCID: https://orcid.org/0009-0000-3065-8899)
- Nichole Wonderling (ORCID: https://orcid.org/0000-0001-6866-2607)
- Jarrett D. Dillenburger (ORCID: https://orcid.org/0000-0001-8274-6452)
- Leanna Schulte (ORCID: https://orcid.org/0000-0002-6970-8811)
- Thomas E. Mallouk (ORCID: https://orcid.org/0000-0003-4599-4208)
- Shihan Qin (ORCID: https://orcid.org/0009-0008-1587-978X)
- Chulsung Bae (ORCID: https://orcid.org/0000-0002-9026-3319)
- Christy George (ORCID: https://orcid.org/0000-0002-6273-8081)
- Andrew M. Rappe (ORCID: https://orcid.org/0000-0003-4620-6496)
- Akshay Venkatesh (ORCID: https://orcid.org/0000-0003-1648-484X)
- Heemin Park (ORCID: https://orcid.org/0000-0001-5164-1551)
- M. Ishak
- Sariah Marth
Institutions
- Pennsylvania State University (US)
- Rensselaer Polytechnic Institute (US)
- National Institute for Materials Science (JP)
- University of Pennsylvania (US)
Publication Details
- Journal
- Chemistry of Materials
- Published
- 2024-11-26
- DOI
- https://doi.org/10.1021/acs.chemmater.4c02082
- Citations
- 4
- Primary Topic
- Transition Metal Oxide Nanomaterials
- Type
- article
- Field-Weighted Citation Impact
- 0.67
Funders
- National Science Foundation
- U.S. Department of Energy
- University of Pennsylvania
- National Energy Research Scientific Computing Center
- Office of Science
- Materials Research Science and Engineering Center, Harvard University
- Division of Materials Research
- Basic Energy Sciences
- Lawrence Berkeley National Laboratory