Ru‐P Nanoalloy from Elemental Phosphorus as P‐Source: Synthesis, Characterization and Catalytic Evaluation

Abstract

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A Simple and Versatile Approach for the Low‐Temperature Synthesis of Transition Metal Phosphide Nanoparticles from Metal Chloride Complexes and P(SiMe3)3

“…Similar resonances have been observed previously in a study in which Ru x P 100-x NPs were synthesized using white phosphorus as P-source and assigned to species with lower local Ru content around the phosphorus nuclei (155 ppm) and oxidized species (−21 ppm). [29] The 31 P WURST-CPMG spectrum of the Ru x P 100-x NPs reported previously [29] is quite similar to the one reported here (Figure 6a), also featuring the high-ppm species assigned to Ru x P 100-x NPs. To probe the effect of oxidation on the samples, a part of the sample was exposed to air for 28 days.…”

Highly Active and Sulfur-Tolerant Ruthenium Phosphide Catalyst for Efficient Reductive Amination of Carbonyl Compounds

“…The P 2p spectrum of Ru 2 P/C exhibited two peaks around 130 and 134 eV, each further resolved into two distinct peaks (Figure d). The peaks that appeared at 129.9 and 131.0 eV were assigned to metal phosphide species, while the other peaks at 135.0 and 133.8 eV represented phosphate species. , These results suggest the presence of not only metallic Ru 2 P but also phosphate species on the surface of Ru 2 P or carbon, potentially originating from the partial decomposition of the phosphorus reagent …”

“…The peaks that appeared at 129.9 and 131.0 eV were assigned to metal phosphide species, 64 while the other peaks at 135.0 and 133.8 eV represented phosphate species. 18,67 These results suggest the presence of not only metallic Ru 2 P but also phosphate species on the surface of Ru 2 P or carbon, potentially originating from the partial decomposition of the phosphorus reagent. 68 The catalytic activity of Ru 2 P/C was assessed with a reference catalyst of Ru/C in the reductive amination of acetophenone (1a) under relatively mild conditions (H 2 (3 bar) and NH 3 (2 bar) mixed gas) at 100 °C for 1 h. Ru 2 P/C selectively promoted the amination of 1a to give the desired primary amine, 1-phenylethylamine (2a), in 59% yield with 95% selectivity (Table 1, entry 1).…”

Direct Determination of Carrier Parameters in Indium Tin Oxide Nanocrystals

“…119 Sn is the most suitable tin isotope for NMR experiments because among the three spin I = 1/2 isotopes ( 115 Sn, 117 Sn and 119 Sn) it has the highest sensitivity. However, being a heavy atom, it usually manifests large magnetic shielding anisotropies and in conducting and semiconducting materials it is also affected by the hyperfine interaction with free electrons, which can shift and broaden the signals and strongly shorten the spin–lattice relaxation time T 1 . − These interactions, which can heavily broaden the SSNMR peaks together with the relatively low 119 Sn sensitivity, often make 119 Sn SSNMR experiments quite challenging. Moreover, working on NCs induces further peak-broadening effects, since the nanosize and the high surface-to-volume ratio make surface effects particularly important. ,, Nevertheless, 119 Sn SSNMR proved to be very successful in investigating the structural and electronic properties of complex conducting and semiconducting materials. ,− As far as ITO is concerned, while several structural models, for bulk or films, have been proposed, , only a few experimental studies, based on 119 Sn Mössbauer spectroscopy, XRD, EXAFS, neutron diffraction, and SSNMR, have been reported in the literature. ,,− …”