Campus Units

Chemistry, Ames Laboratory

Document Type

Article

Publication Version

Submitted Manuscript

Publication Date

2-11-2021

Journal or Book Title

Journal of Physical Chemistry C

Volume

125

Issue

5

First Page

2956

Last Page

2965

DOI

10.1021/acs.jpcc.0c09601

Abstract

Indium phosphide quantum dots (InP QD) are a promising alternative to traditional QD materials that contain toxic heavy elements such as lead and cadmium. However, InP QD obtained from colloidal synthesis are often plagued by poor photoluminescence quantum yields (PL-QYs). In order to improve the PL-QY of InP QD, a number of post-synthetic treatments have been devised. Recently, it has been shown that InP post-synthetically treated with Lewis acid metal divalent cations (M-InP) exhibit enhanced PL-QY; however, the molecular structure and mechanism behind the improved PL-QY are not fully understood. To determine the surface structure of M-InP QD, dynamic nuclear polarization surface-enhanced nuclear magnetic resonance spectroscopy (DNP SENS) experiments were employed on a series of InP magic size clusters treated with Cd ions, InP QD, cadmium phosphide (Cd3P2) QD, and Cd-treated InP QD (Cd–InP QD). With the use of DNP SENS, we were able to obtain the 1D 31P and 113Cd NMR spectra, 113Cd{31P} rotational-echo double-resonance (REDOR) NMR spectra, and 31P{113Cd} dipolar heteronuclear multiple quantum correlation (D-HMQC) sequence. Changes in the phosphide 31P chemical shifts after Cd treatment provide indirect evidence that some Cd alloys into the sub-surface regions of the particle. DNP-enhanced 113Cd solid-state NMR spectra suggest that most Cd ions are coordinated by oxygen atoms from either carboxylate ligands or surface phosphate groups. 113Cd{31P} REDOR and 31P{113Cd} D-HMQC experiments confirm that a subset of Cd ions are located on the surface of Cd–InP QD and coordinated with phosphate groups.

Comments

This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in Journal of Physical Chemistry C, copyright © American Chemical Society after peer review. To access the final edited and published work see DOI: 10.1021/acs.jpcc.0c09601. Posted with permission.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Published Version

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