Mechanistic insights into the formation of hydroxides with unconventional coordination environments to achieve their cost-effective synthesis
Transition metal hydroxides, comprising metal-centered polyhedra, are abundant in nature and have a broad range of applications. Although the intercalation/deintercalation of polyhedra with unconventional coordination numbers (UCN) plays a pivotal role in their formation process and influences their chemical behavior, the detailed mechanism remains obscure. Here, taking the kinetically controlled growth of Co(OH)<sub>2</sub> as a model system (where polyhedra with UCN refers to 4-coordinated tetrahedra), by combining <i>in situ</i> pH measurement and <i>in situ</i> ultraviolet-visible (UV-vis) spectroscopy, we tracked Co<sup>2+</sup> tetrahedral intercalation/deintercalation with varying OH<sup>-</sup> concentrations, discovering that the initial Co<sup>2+</sup> tetrahedral intercalation into the Co(OH)<sub>2</sub> lattice is inevitable and its retention is influenced by the effective OH<sup>-</sup> concentration, challenging previous beliefs about the formation of Co(OH)<sub>2</sub> and potentially other hydroxides. More importantly, an understanding of the intercalation mechanism would significantly contribute to optimization of the synthesis conditions of hydroxides with tunable coordination environments, which hold significant application potential, as evidenced by a proof-of-concept application in the oxygen evolution reaction.
Authors
- Liqun Kang (ORCID: https://orcid.org/0000-0003-2100-4310)
- Saskia Heumann (ORCID: https://orcid.org/0000-0003-3594-6392)
- Zongkun Chen (ORCID: https://orcid.org/0000-0002-8993-8681)
- Wenchao Wan (ORCID: https://orcid.org/0000-0003-2358-016X)
- Minghua Huang (ORCID: https://orcid.org/0000-0002-9622-3131)
- Jonathan Avaro (ORCID: https://orcid.org/0000-0001-6596-3228)
- Xingkun Wang
- Serena DeBeer (ORCID: https://orcid.org/0000-0002-5196-3400)
- Helmut Cölfen (ORCID: https://orcid.org/0000-0002-1148-0308)
- Qiqi Fan
- Christina Scheu (ORCID: https://orcid.org/0000-0001-7916-1533)
- Siyuan Zhang (ORCID: https://orcid.org/0000-0001-7045-0865)
- Jian Zhou (ORCID: https://orcid.org/0000-0001-7551-0230)
- Heqing Jiang (ORCID: https://orcid.org/0000-0002-8061-4816)
Institutions
- University of Konstanz (DE)
- Chinese Academy of Sciences (CN)
- University of St.Gallen (CH)
- Max-Planck-Institut für Nachhaltige Materialien (DE)
- Max Planck Institute for Chemical Energy Conversion (DE)
- University of Applied Sciences St. Gallen (CH)
- Qingdao Institute of Bioenergy and Bioprocess Technology (CN)
- Ocean University of China (CN)
- Swiss Federal Laboratories for Materials Science and Technology (CH)
Publication Details
- Journal
- National Science Review
- Published
- 2024-12-23
- DOI
- https://doi.org/10.1093/nsr/nwae427
- Citations
- 2
- Primary Topic
- Layered Double Hydroxides Synthesis and Applications
- Type
- article
- Field-Weighted Citation Impact
- 0.23
Funders
- Alexander von Humboldt-Stiftung
- Deutsche Forschungsgemeinschaft
- National Natural Science Foundation of China
- Max-Planck-Gesellschaft
- Deutsches Elektronen-Synchrotron