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Gas diffusion electrodes on the electrosynthesis of controllable iron oxide nanoparticles

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2019

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Nature Publishing Group
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The electrosynthesis of iron oxide nanoparticles offers a green route, with significant energy and environmental advantages. Yet, this is mostly restricted by the oxygen solubility in the electrolyte. Gas-diffusion electrodes (GDEs) can be used to overcome that limitation, but so far they not been explored for nanoparticle synthesis. Here, we develop a fast, environmentally-friendly, room temperature electrosynthesis route for iron oxide nanocrystals, which we term gas-diffusion electrocrystallization (GDEx). A GDE is used to generate oxidants and hydroxide in-situ, enabling the oxidative synthesis of a single iron salt (e.g., FeCl_2) into nanoparticles. Oxygen is reduced to reactive oxygen species, triggering the controlled oxidation of Fe^(2+) to Fe^(3+), forming Fe_(3-x)O_(4-x) (0 <= x <= 1). The stoichiometry and lattice parameter of the resulting oxides can be controlled and predictively modelled, resulting in highly-defective, strain-heavy nanoparticles. The size of the nanocrystals can be tuned from 5 nm to 20 nm, with a large saturation magnetization range (23 to 73 A m^2 kg^(-1)), as well as minimal coercivity (similar to 1 kA m^(-1)). Using only air, NaCl, and FeCl_2, a biocompatible approach is achieved, besides a remarkable level of control over key parameters, with a view on minimizing the addition of chemicals for enhanced production and applications.

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©2019 Nature Publishing Group R.P. acknowledges VITO Strategic PhD grant funding No. 1510774. R.P., G.P., J.F. and X.D.B. thank the support from the Flemish SIM MaRes programme, under grant agreement No. 150626 (Get-A-Met project). X.D.B. and J.F. thanks the funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No. 654100 (CHPM2030 project). G. Pozo acknowledges the funding from the European Union's Horizon 2020 research and innovation programme MSCA-IF-2017, under grant agreement No. 796320 (MAGDEx: Unmet MAGnetic properties in micro and nano-particles by synthesis through gas diffusion electrocrystallisation, (GDEx). This work has been supported by the Ministerio Espanol de Economia y Competitividad (MINECO) MAT201567557-C2-1-P, and Comunidad de Madrid S2013/MIT-2850 NANOFRONTMAG projects. We would also like to acknowledge Myriam Mertens for fruitful discussions and her support on XRD analysis, as well as Kristof Tirez and Wilfried Brusten for assistance with analytical measurements. We thank Dr. Vitaliy Bliznuk (UGent, Electron microscopy laboratory) for assisting in TEM analysis.

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