Cation Extraction Process in Bilayer Cyanide Film as Investigated by Depth-Resolved X-ray Absorption Spectroscopy

Environmental context. Very fine phosphor ashes are discharged from particulate collection systems (such as bag houses) in the cathode ray tube or television disassembling processes. Effective recovery of ZnO and ZnS nanoparticles from the phosphor ash can be achieved by extraction with a room temperature ionic liquid. By synchrotron radiation X-ray absorption spectroscopy, the obtained molecular scale data turn out to be very useful in revealing speciation of zinc in the extraction process, which also facilitates the development of a simple nanoparticle recovery method. Abstract. An effective, simple method has been developed for the recovery of ZnO and ZnS nanoparticles from hazardous phosphor ash waste. Experimentally, zinc (77%) in the phosphor ash (that contains mainly zinc (91%)) can be recovered by extraction with a room temperature ionic liquid (RTIL) ([C4mim][PF6], 1-butyl-3-methylimidazolium hexafluorophosphate). Component fitted X-ray absorption near edge structure (XANES) spectra of zinc indicate that metallic zinc (Zn) (9%) in the phosphor ash can be dissolved to form a Zn2+–1-methylimidazole ([mim]) complex during extraction with the RTIL. ZnS and ZnO nanoparticles (60–61%) can also be extracted from the phosphor. Over the 298–523 K temperature range, desired ZnO/ZnS ratios (0.3–0.6) can be obtained since interconversion of ZnS to ZnO in the RTIL is temperature dependent. The Fourier transformed extended X-ray absorption fine structure (EXAFS) data also show that the nanosize ZnS extracted in the RTIL possesses a Zn–S bond distance of 2.33 Å with coordination numbers (CNs) of 3.6–3.7. At 523 K, in the RTIL, ~30% of the ZnS is oxidised to form octahedral ZnO (with a bond distance of 2.10 Å and a CN of 6.1) that may coat the surfaces of the ZnS nanoparticles. This work exemplifies the utilisation of X-ray absorption spectroscopy (EXAFS and XANES) to reveal speciation and possible reaction pathways in a nanoparticle extraction process (with a RTIL) in detail.

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Characterization of the Electrochemical Reactions in the Li1+xV3O8/Li Cell by Soft X-ray Absorption Spectroscopy and Two-Dimensional Correlation Analysis

Applied Spectroscopy ◽

10.1366/000370203322258959 ◽

2003 ◽

Vol 57 (8) ◽

pp. 984-990 ◽

Cited By ~ 12

Author(s):

Hyun Chul Choi ◽

Young Mee Jung ◽

Seung Bin Kim

Keyword(s):

Correlation Analysis ◽

Absorption Spectroscopy ◽

Extraction Process ◽

Electrochemical Reactions ◽

Lithium Content ◽

Spectral Features ◽

Two Dimensional ◽

X Ray ◽

X Ray Absorption ◽

2D Correlation Analysis

We applied soft X-ray absorption spectroscopy (XAS) and two-dimensional (2D) correlation analysis to the first lithium insertion–extraction cycle in a Li1+xV3O8/Li cell in order to investigate the electrochemical reactions of lithium with the Li1+xV3O8 electrode. The V LII,III-edge and O K-edge spectra of the Li1+xV3O8 electrode were obtained for varying electrode lithium content. The insertion of lithium leads to the reduction of the V5+ species present in the pristine Li1+xV3O8 electrode, and to the red shift and the broadening of the spectral features of the V LII,III edge compared to those of the pristine electrode. In the extraction process, the main spectral features at the highest value of the extraction of lithium show some differences compared to the features of the pristine electrode spectrum due to the residual lithium ions in the Li1+xV3O8 structure. The O K-edge spectra revealed that the insertion of lithium mainly affects the V 4sp–O 2p bonds and consequently induces a change in bonding geometry. The 2D correlation analysis of these spectra clearly shows that V–O bonds are significantly perturbed by the insertion–extraction of lithium into the Li1+xV3O8 electrode.

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