Observation of Low-γ Quadrupolar Nuclei by Surface-Enhanced NMR Spectroscopy.

We introduce a novel NMR approach that extends the capabilities of indirect dynamic nuclear polarization (DNP) under magic-angle spinning to probe the local environment of half-integer spin quadrupolar nuclei. Compared to cross-polarization, this novel method based on the refocused INEPT scheme with adiabatic dipolar recoupling is easier to optimize and does not distort the quadrupolar line shapes. Furthermore, the use of this technique, instead of the PRESTO (Phase-shifted Recoupling Effects a Smooth Transfer of Order) scheme or direct DNP, greatly improves the sensitivity of DNP-NMR for the detection of quadrupolar isotopes with small dipolar couplings to protons, including notably those located in the subsurface of inorganic materials or with low gyromagnetic ratio (γ). This technique has been applied to identify the atomic-level structure of Brønsted acid sites of hydrated titania-supported MoO3, MoO3/TiO2, a widely used heterogeneous catalyst. The spectra of protonated and unprotonated 17O sites, acquired in natural abundance, indicate the presence of various oxomolybdate species as well as HOMo2 and HOMo3 Brønsted acid sites. The enhanced sensitivity of this new method has also enabled the acquisition of the first DNP-enhanced spectra of 95Mo and 47,49Ti low-γ quadrupolar isotopes. This possibility has been demonstrated by detecting the signals of these nuclei near the surface of MoO3/TiO2. This technique has allowed the observation of 49Ti surface sites, which are absent from the bulk region of TiO2. Furthermore, both 95Mo and 47,49Ti DNP spectra have shown an increased structural disorder of TiO2 and MoO3 phases near the surface of the particles and notably the preferential location of the amorphous TiO2 phase at the surface of the particles. The proposed polarization transfer is also employed to acquire the first DNP-enhanced spectrum of 67Zn, another low-γ quadrupolar isotope. This possibility is demonstrated for Al-doped ZnO nanoparticles used in optoelectronic devices. The obtained 17O, 27Al, and 67Zn DNP-NMR data prove that the surface region of these nanoparticles contains ZnO phase as well as secondary phases, such as α-Al2O3 and partially inverse ZnAl2O4 spinel.