4.8 Article

Gallium-Based Liquid Metal Reaction Media for Interfacial Precipitation of Bismuth Nanomaterials with Controlled Phases and Morphologies

Journal

ADVANCED FUNCTIONAL MATERIALS
Volume 32, Issue 8, Pages -

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/adfm.202108673

Keywords

bismuth oxide; liquid-liquid interface; metal expulsion; phase separation; post transition metals

Funding

  1. Australian Research Council (ARC) Laureate Fellowship [FL180100053]
  2. ARC Center of Excellence FLEET [CE170100039]
  3. DECRA grant [DE210101259]
  4. ARC [DE180100215]
  5. Australian Research Council [DE180100215] Funding Source: Australian Research Council

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The study demonstrates that applying a negative voltage to the interface between liquid alloys and aqueous electrolytes can rapidly liberate bismuth nanostructures, with the oxidation state, morphology, and crystal structure of the expelled bismuth being controllable by adjusting a set of conditions; addition of ascorbic acid can prevent oxidation and produce bismuth metal nanoparticles. Molecular dynamics simulations help elucidate the rapid phase separation at the interface, potentially opening up new pathways for refining metals and producing nanomaterials using alloys as reaction media.
Liquid-liquid interfaces of liquid alloys with electrolytic solutions present fertile platforms for realizing exciting interfacial phenomena that can be devised to process alloys and produce nanomaterials. Here, such an interface is established by immersing a gallium-bismuth binary liquid alloy into aqueous electrolytes. It is shown that the application of a negative voltage to this interface results in a rapid and complete liberation of bismuth nanostructures from liquid gallium. The set of conditions that govern the chemistry of the interface can be adjusted to control the oxidation state, morphology, and crystal structure of the expelled bismuth. By changing the conditions; nanotubular, atomically thin plates, and sea-urchin-shaped bismuth oxide morphologies are obtained. The process can also control the crystal phase of bismuth oxide as monoclinic (alpha), tetragonal (beta), or body-centered cubic (gamma). The addition of ascorbic acid to the electrolyte is observed to prevent the oxidation of the expelled entities, resulting in bismuth metal nanoparticles. Ab initio molecular dynamics and computational fluid dynamics simulations are performed to elucidate this rapid phase separation at the interface. This knowledge will potentially lead to new pathways for using alloys as reaction media to refine metals while simultaneously producing nanomaterials for various applications.

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