Abstract
Low-temperature electrodeposition strategies to obtain lanthanides in metallic form using ionic liquids are explored as sustainable substitutes to high-temperature molten salt electrolytes. Herein, we report the electrochemical behaviour of samarium(III) and the electrodeposition of samarium in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, ionic liquid. Raman spectroscopic analysis indicated the existence of
Sm
(
T
f
2
N
)
4
−
complex in as-prepared electrolyte. Trivalent samarium species undergoes two-step reduction via Sm(III)↔Sm(II) at –1.0 V and Sm(II)→Sm(0) at –2.1 V with the corresponding oxidation peaks observed at potentials ∼+1.0 V and +1.9 V vs Ag/Ag+, respectively, and attributed to the stripping of zero-valent samarium to Sm(II) which subsequently undergoes re-oxidation to Sm(III) species, respectively. Diffusion coefficient of Sm(III) species increases from 1.75 × 10−7 at 343 K to 6.27 × 10−7 cm2 s−1 at 373 K due to decrease in the electrolyte viscosity and activation energy (Ea) was determined to be 42 kJ mol−1. Samarium electrodeposited at −2.5 V vs Ag/Ag+ was ∼3-micron thick coating with visible crack. XPS analysis provided qualitative proof for elemental samarium in the deposit co-existing with its oxide film likely due to exposure to atmosphere during analysis. The present study demonstrates the possibility to electrodeposit samarium using [BMP][Tf2N] ionic liquid at near ambient conditions.
Funder
Council for Scientific and Industrial Research
Science and Engineering Research Board
Publisher
The Electrochemical Society
Subject
Materials Chemistry,Electrochemistry,Surfaces, Coatings and Films,Condensed Matter Physics,Renewable Energy, Sustainability and the Environment,Electronic, Optical and Magnetic Materials
Cited by
3 articles.
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