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Mechanistic insight into copper cation exchange in cadmium selenide semiconductor nanocrystals using X-ray absorption spectroscopy.

Nature communications (2021-01-21)
Alex Khammang, Joshua T Wright, Robert W Meulenberg
ABSTRACT

In terms of producing new advances in sustainable nanomaterials, cation exchange (CE) of post-processed colloidal nanocrystals (NCs) has opened new avenues towards producing non-toxic energy materials via simple chemical techniques. The main processes governing CE can be explained by considering hard/soft acid/base theory, but the detailed mechanism of CE, however, has been debated and has been attributed to both diffusion and vacancy processes. In this work, we have performed in situ x-ray absorption spectroscopy to further understand the mechanism of the CE of copper in solution phase CdSe NCs. The x-ray data indicates clear isosbestic points, suggestive of cooperative behavior as previously observed via optical spectroscopy. Examination of the extended x-ray absorption fine structure data points to the observation of interstitial impurities during the initial stages of CE, suggesting the diffusion process is the fundamental mechanism of CE in this system.

MATERIALS
Product Number
Brand
Product Description

Sigma-Aldrich
Tetrakis(acetonitrile)copper(I) hexafluorophosphate, 97%
Sigma-Aldrich
Trioctylphosphine oxide, ReagentPlus®, 99%
Sigma-Aldrich
Cadmium carbonate, powder, 98%