Structural and morphological control of crystalline nanoparticles is crucial in the field of heterogeneous catalysis and the development of reaction specific catalysts. To achieve this, colloidal chemistry methods are combined with ab initio calculations in order to define the reaction parameters, which drive chemical reactions to the desired crystal nucleation and growth path. Key in this procedure is the experimental verification of the predicted crystal facets and their corresponding electronic structure, which in case of nanostructured materials becomes extremely difficult. Here, by employing P-31 solid-state nuclear magnetic resonance aided by advanced density functional theory calculations to obtain and assign the Knight shifts, we succeed in determining the crystal and electronic structure of the terminating surfaces of ultrafine Ni2P nanoparticles at atomic scale resolution. Our work highlights the potential of ssNMR nanocrystallography as a unique tool in the emerging field of facet-engineered nanocatalysts. Structural and morphological control of crystalline nanoparticles is crucial in heterogeneous catalysis. Applying DFT-assisted solid-state NMR spectroscopy, we determine the surface crystal and electronic structure of Ni2P nanoparticles, unveiling NMR nanocrystallography as an emerging tool in facet-engineered nanocatalysts.

Highly mesoporous SiO2-encapsulated NixPy crystals, where (x, y) = (5, 4), (2, 1), and (12, 5), were successfully synthesized by adopting a thermolytic method using oleylamine (OAm), trioctylphosphine (TOP), and trioctylphosphine oxide (TOPO). The Ni5P4@SiO2 system shows the highest reported activity for the selective hydrogenation of SO2 toward H2S at 320 degrees C (96% conversion of SO2 and 99% selectivity to H2S), which was superior to the activity of the commercial CoMoS@Al2O3 catalyst (64% conversion of SO2 and 71% selectivity to H2S at 320 degrees C). The morphology of the Ni5P4 crystal was finely tuned via adjustment of the synthesis parameters receiving a wide spectrum of morphologies (hollow, macroporous-network, and SiO2-confined ultrafine clusters). Intrinsic characteristics of the materials were studied by Xray diffraction, high-resolution transmission electron microscopy/scanning transmission electron microscopy-high-angle annular dark-field imaging, energydispersive X-ray spectroscopy, the Brunauer-Emmett-Teller method, H-2 temperature-programmed reduction, X-ray photoelectron spectroscopy, and experimental and calculated P-31 magic-angle spinning solid-state nuclear magnetic resonance toward establishing the structure-performance correlation for the reaction of interest. Characterization of the catalysts after the SO2 hydrogenation reaction proved the preservation of the morphology, crystallinity, and Ni/P ratio for all the catalysts.

Weyl Fermions (WFs) in the type-II Weyl Semimetal (WSM) WTe2 are difficult to resolve experimentally because the Weyl bands disperse in an extremely narrow region of the (E-k) space. Here, by using DFT-assisted high-resolution 125Te solid-state NMR (ssNMR) in the temperature range 50K - 700K, we succeeded in detecting low energy WF excitations and monitor their evolution with temperature. Remarkably, WFs appear to emerge at T∼120K; at lower temperatures WTe2 behaves as a metal. This intriguing metal-to-WSM phase transition is shown to be induced by the rapid raise of the Fermi level with temperature, crossing solely the electron and hole pockets in the low-T metallic phase, while crossing the Weyl bands near the nodal points - a prerequisite for the emergence of WFs - only for T>120K.

Detecting the metallic Dirac electronic states on the surface of Topological Insulators (TIs) is critical for the study of important surface quantum properties (SQPs), such as Majorana zero modes, where simultaneous probing of the bulk and edge electron states is required. However, there is a particular shortage of experimental methods, showing at atomic resolution how Dirac electrons extend and interact with the bulk interior of nanoscaled TI systems. Herein, by applying advanced broadband solid-state 125Te nuclear magnetic resonance (NMR) methods on Bi2Te3 nanoplatelets, we succeeded in uncovering the hitherto invisible NMR signals with magnetic shielding that is influenced by the Dirac electrons, and we subsequently showed how the Dirac electrons spread inside the nanoplatelets. In this way, the spin and orbital magnetic susceptibilities induced by the bulk and edge electron states were simultaneously measured at atomic scale resolution, providing a pertinent experimental approach in the study of SQPs.

Tetradymite-type (Bi2Te2S) structures and their analogues (P2X3, where P = Sb,Bi and X = S, Se, Te) have recently garnered attention as interesting materials as potential anodes in Li- and Na-ion batteries. As of now, potential mechanisms of the electrochemical cycle are conflicting, as both intercalation of the ion followed by a conversion and an alloying reaction, or a conversion followed by an alloying reaction straight up have been reported. It is, thus, of importance to determine the exact phases that are being produced during each reaction step, in order to optimize the conditions, under which these structures can thrive as anodes. In this study, we succeed this, by employing a combination of ex-situ solid-state nuclear magnetic resonance (ssNMR) and transmission electron microscopy (TEM), during various points during the first discharge and subsequent charge of microcrystalline Bi2Te3. The results are aided by density functional theory calculations (DFT) of the NMR Knight shifts and the electronic structure of all phases present during the cycle. This highlights the ability of solid-state NMR to monitor the phase evolution during cycling of electronically non-trivial systems.