Observing the Surface Termination of LaScO Perovskite Using Solid-State Nuclear Magnetic Resonance.

Materials with well-defined surfaces are drawing increased attention for the design of bespoke catalysts and nanomaterials. Gaining a detailed understanding of the surfaces of these materials is an important challenge, which is often complicated by surface polymorphism and dynamic restructuring. We introduce the use of surface-enhanced NMR spectroscopy for the observation of such surfaces, focusing on LaScO as an example.

Are the Brønsted acid sites in amorphous silica-alumina bridging?

Competing models exist to explain the differences in the activity of zeolites and amorphous silica-aluminas. Some postulate that silica-alumina contains dilute zeolitic bridging acid sites, while others favor a pseudo-bridging silanol model. We employed a selective isotope labeling strategy to assess the existence of Si-O(H)-Al bonds using NMR-based distance measurements.

Surfactants Used in Colloidal Synthesis Modulate Ni Nanoparticle Surface Evolution for Selective CO Hydrogenation.

Colloidal chemistry holds promise to prepare uniform and size-controllable pre-catalysts; however, it remains a challenge to unveil the atomic-level transition from pre-catalysts to active catalytic surfaces under the reaction conditions to enable the mechanistic design of catalysts. Here, we report an ambient-pressure X-ray photoelectron spectroscopy study, coupled with in situ environmental transmission electron microscopy, infrared spectroscopy, and theoretical calculations, to elucidate the surface catalytic sites of colloidal Ni nanoparticles for CO hydrogenation. We show that Ni nanoparticles with phosphine ligands exhibit a distinct surface evolution compared with amine-capped ones, owing to the diffusion of P under oxidative (air) or reductive (CO + H) gaseous environments at elevated temperatures.

Mesoporous Silica Encapsulated Platinum-Tin Intermetallic Nanoparticles Catalyze Hydrogenation with an Unprecedented 20% Pairwise Selectivity for Parahydrogen Enhanced Nuclear Magnetic Resonance.

Supported noble metals offer key advantages over homogeneous catalysts for in vivo applications of parahydrogen-based hyperpolarization. However, their performance is compromised by randomization of parahydrogen spin order resulting from rapid hydrogen adatom diffusion. The diffusion on Pt surfaces can be suppressed by introduction of Sn to form Pt-Sn intermetallic phases.

Pairwise semi-hydrogenation of alkyne to cis-alkene on platinum-tin intermetallic compounds.

The molecular basis for the high cis-alkene selectivity over intermetallic PtSn for alkyne semi-hydrogenation is demonstrated. Unlike the universal assumption that the bimetallic surface is saturated with atomic hydrogen, molecular hydrogen has a higher barrier for dissociative adsorption on intermetallic PtSn due to the deficiency of Pt three-fold sites. The resulting molecular behavior of adsorbed hydrogen on intermetallic PtSn nanoparticles leads to pairwise-hydrogenation of three alkynes to the corresponding cis-alkenes, satisfying both high stereoselectivity and high chemoselectivity.

Atomic-Scale Structure of Mesoporous Silica-Encapsulated Pt and PtSn Nanoparticles Revealed by Dynamic Nuclear Polarization- Enhanced 29Si MAS NMR Spectroscopy.

Mesoporous silica encapsulated Pt (Pt@mSiO) and PtSn (PtSn@mSiO) nanoparticles (NPs) are representatives of a novel class of heterogeneous catalysts with uniform particle size, enhanced catalytic properties, and superior thermal stability. In the ship-in-a-bottle synthesis, PtSn@mSiO intermetallic NPs are derived from Pt@mSiO seeds where the mSiO shell is formed by polymerization of tetraethyl orthosilicate around a tetradecyltrimethylammonium bromide template, a surfactant used to template MCM-41. Incorporation of Sn into the Pt@mSiO seeds is accommodated by chemical etching of the mSiO shell.