Elucidating the Location of Cd2+ in Post-synthetically Treated InP Quantum Dots Using Dynamic Nuclear Polarization 31P and 113Cd Solid-State NMR Spectroscopy

Hanrahan, Michael P.; Stein, Jennifer L.; Park, Nayon; Cossairt, Brandi M.; Rossini, Aaron J.

doi:10.1021/acs.jpcc.0c09601

Title: Elucidating the Location of Cd²⁺ in Post-synthetically Treated InP Quantum Dots Using Dynamic Nuclear Polarization ³¹P and ¹¹³Cd Solid-State NMR Spectroscopy

Journal Article · Wed Jan 27 00:00:00 EST 2021 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.0c09601· OSTI ID:1764374

Hanrahan, Michael P. ^[1];

^[2]; Park, Nayon ^[2];

^[2];

^[1]

Iowa State Univ., Ames, IA (United States); Ames Lab., Ames, IA (United States)
Univ. of Washington, Seattle, WA (United States)

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. Here, 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.

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Research Organization:: Ames Lab., Ames, IA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; Alfred P. Sloan Foundation; National Science Foundation (NSF)

Grant/Contract Number:: AC02-07CH11358

OSTI ID:: 1764374

Report Number(s):: IS-J-10,405

Journal Information:: Journal of Physical Chemistry. C, Vol. 125, Issue 5; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Elucidating the Location of Cd ²⁺ in Post-synthetically Treated InP Quantum Dots Using Dynamic Nuclear Polarization ³¹ P and ¹¹³ Cd Solid-State NMR Spectroscopy Hanrahan, Michael P.; Stein, Jennifer L.; Park, Nayon The Journal of Physical Chemistry C, Vol. 125, Issue 5 https://doi.org/10.1021/acs.jpcc.0c09601	journal	January 2021

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Quantum dots
Inorganic compounds
Phosphates
Quantum mechanics
Nuclear magnetic resonance spectroscopy

Title: Elucidating the Location of Cd2+ in Post-synthetically Treated InP Quantum Dots Using Dynamic Nuclear Polarization 31P and 113Cd Solid-State NMR Spectroscopy

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Title: Elucidating the Location of Cd²⁺ in Post-synthetically Treated InP Quantum Dots Using Dynamic Nuclear Polarization ³¹P and ¹¹³Cd Solid-State NMR Spectroscopy