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The chemical versatility and rich phase behavior of tin phosphides has led to interest in their use for a wide range of applications including optoelectronics, thermoelectrics, and electrocatalysis. However, researchers have identified few viable routes to high-quality, phase-pure, and phase-controlled tin phosphides. An outstanding issue is the small library of phosphorus precursors available for synthesis of metal phosphides. We demonstrated that inexpensive, commercially available, and environmentally benign aminophosphines can generate various phases of colloidal tin phosphides. We manipulated solvent concentrations, precursor identities, and growth conditions to obtain Sn 3 P 4 , SnP, and Sn 4 P 3 nanocrystals. We performed a combination of X-ray diffraction and transmission electron microscopy to determine the phase purity of our samples. X-ray absorption spectroscopy provided detailed analyses of the local structures of the tin phosphides. 

Atomically dispersed and nitrogen-coordinated single Ni sites ( i.e. , NiN x moieties) embedded in partially graphitized carbon have emerged as effective catalysts for CO 2 electroreduction to CO. However, much mystery remains behind the extrinsic and intrinsic factors that govern the overall catalytic CO 2 electrolysis performance. Here, we designed a high-performance single Ni site catalyst through elucidating the structural evolution of NiN x sites during thermal activation and other critical external factors ( e.g. , carbon particle sizes and Ni content) by using Ni–N–C model catalysts derived from nitrogen-doped carbon carbonized from a zeolitic imidazolate framework (ZIF)-8. The N coordination, metal–N bond length, and thermal wrinkling of carbon planes in Ni–N–C catalysts significantly depend on thermal temperatures. Density functional theory (DFT) calculations reveal that the shortening Ni–N bonds in compressively strained NiN 4 sites could intrinsically enhance the CO 2 RR activity and selectivity of the Ni–N–C catalyst. Notably, the NiN 3 active sites with optimal local structures formed at higher temperatures ( e.g. , 1200 °C) are intrinsically more active and CO selective than NiN 4 , providing a new opportunity to design a highly active catalyst via populating NiN 3 sites with increased density. We also studied how morphological factors such as the carbon host particle size and Ni loading alter the final catalyst structure and performance. The implementation of this catalyst in an industrial flow-cell electrolyzer demonstrated an impressive performance for CO generation, achieving a current density of CO up to 726 mA cm −2 with faradaic efficiency of CO above 90%, representing one of the best catalysts for CO 2 reduction to CO. 

Despite the well-known tendency for many alloys to undergo ordering transformations, the microscopic mechanism of ordering and its dependence on alloy composition remains largely unknown. Using the example of Pt 85 Fe 15 and Pt 65 Fe 35 alloy nanoparticles (NPs), herein we demonstrate the composition-dependent ordering processes on the single-particle level, where the nanoscale size effect allows for close interplay between surface and bulk in controlling the phase evolution. Using in situ electron microscopy observations, we show that the ordering transformation in Pt 85 Fe 15 NPs during vacuum annealing occurs via the surface nucleation and growth of L1 2 -ordered Pt 3 Fe domains that propagate into the bulk, followed by the self-sacrifice transformation of the surface region of the L1 2 Pt 3 Fe into a Pt skin. By contrast, the ordering in Pt 65 Fe 35 NPs proceeds via an interface mechanism by which the rapid formation of an L1 0 PtFe skin occurs on the NPs and the transformation boundary moves inward along with outward Pt diffusion. Although both the “nucleation and growth” and the “interface” mechanisms result in a core–shell configuration with a thin Pt-rich skin, Pt 85 Fe 15 NPs have an L1 2 Pt 3 Fe core, whereas Pt 65 Fe 35 NPs are composed of an L1 0 PtFe core. Using atomistic modeling, we identify the composition-dependent vacancy-assisted counterdiffusion of Pt and Fe atoms between the surface and core regions in controlling the ordering transformation pathway. This vacancy-assisted diffusion is further demonstrated by oxygen annealing, for which the selective oxidation of Fe results in a large number of Fe vacancies and thereby greatly accelerates the transformation kinetics.