Revealing the Surface Structure of CdSe Nanocrystals by Dynamic Nuclear Polarization-Enhanced ⁷⁷Se and ¹¹³Cd...

Dynamic nuclear polarization (DNP) solid-state NMR (SSNMR) spectroscopy was used to obtain detailed surface structures of zinc blende CdSe nanocrystals (NCs) with plate or spheroidal morphologies which are capped by carboxylic acid ligands. 1D ¹¹³Cd and ⁷⁷Se cross-polarization magic angle spinning (CPMAS) NMR spectra revealed distinct signals from Cd and Se atoms on the surface of the NCs, and those residing in bulk-like environments, below the surface. ¹¹³Cd cross-polarization magic-angle-turning (CP-MAT) experiments identified CdSe₃O, CdSe₂O₂, and CdSeO₃ Cd coordination environments on the surface of the NCs, where the oxygen atoms are presumably from coordinated carboxylate ligands. The sensitivity gain from DNP enabled natural isotopic abundance 2D homonuclear ¹¹³Cd-¹¹³Cd and ⁷⁷Se-⁷⁷Se and heteronuclear ¹¹³Cd-⁷⁷Se scalar correlation solid-state NMR experiments which revealed the connectivity of the Cd and Se atoms. Importantly, ⁷⁷Se{¹¹³Cd} scalar heteronuclear multiple quantum coherence (J-HMQC) experiments were used to selectively measure one-bond ⁷⁷Se-¹¹³Cd scalar coupling constants (¹J(⁷⁷Se, ¹¹³Cd)). With knowledge of ¹J(⁷⁷Se, ¹¹³Cd), heteronuclear ⁷⁷Se{¹¹³Cd} spin echo (J-resolved) NMR experiments were used to determine the number of Cd atoms bonded to Se atoms and vice versa. The J-resolved experiments directly confirmed that major Cd and Se surface species have CdSe₂O₂ and SeCd₄ stoichiometries, respectively. Considering the crystal structure of zinc blende CdSe and the similarity of the solid-state NMR data for the platelets and spheroids, we conclude that the surface of the spheroidal CdSe NCs is primarily composed of {100} facets. The methods outlined here will generally be applicable to obtain detailed surface structures of various main group semiconductor nanoparticles.