Valence-Controlled Flexibility and Gelation in Cerium-Polyoxometalate Subnanowires.
basic_science · Level V
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- Record sourced from PubMed, PMID 42149112.
- Also identified by DOI 10.1021/acs.nanolett.6c00701.
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Abstract
Subnanometer inorganic nanowires (SNWs) exhibit polymer-like flexibility, yet the ability to rationally control their rigidity remains a fundamental challenge. Here we demonstrate that the flexibility of phosphomolybdic acid-cerium oxide hybrid SNWs can be precisely modulated by redox-governed cerium valence transitions. Using time-resolved SAXS, we show that the persistence length of SNWs can be tuned from ∼2452 Å (rigid, Ce<sup>4+</sup>) to ∼20 Å (flexible, Ce<sup>3+</sup>) upon thermal treatment, as verified by XPS. The resulting SNWs form hierarchical gels whose viscoelastic properties scale with nanowire flexibility, with storage moduli ranging from ∼10<sup>4</sup> Pa for semiflexible gels to ∼10<sup>2</sup> Pa for rigid ones. Semiflexible SNWs yield an optimized network that balances entanglement and free volume, leading to relaxation dynamics distinct from classical polymers and colloidal glasses. This work establishes a direct link between inorganic redox chemistry, nanoscale chain flexibility, and macroscopic gel performance, offering a strategy for designing mechanically tunable subnanometer soft materials.