Revealing the Surface Structure of CdSe Nanocrystals by Dynamic Nuclear Polarization-Enhanced 77Se and 113Cd Solid-State NMR Spectroscopy

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 and 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 that reveal 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 then 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 semiconductors.