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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. 

We have successfully synthesized ultrathin nanowires of pure Pt, Pt₉₉Ni₁, Pt₉Ni₁, and Pt₇Ni₃using a modified room‐temperature soft‐template method. Analysis of both methanol oxidation reaction (MOR) and ethanol oxidation reaction (EOR) results found that the Pt₇Ni₃samples yielded the best performance with specific activities of 0.36 and 0.34 mA/cm²respectively. Additionally, formic acid oxidation reaction (FAOR) tests noted that both Pt and PtNi nanowires oxidize small organic molecules (SOMs) via an indirect pathway. CO oxidation data suggests little measurable performance without any pre‐reduction treatment; however, after annealing in H₂, we detected significantly improved CO₂formation for both Pt₉Ni₁and Pt₇Ni₃motifs. These observations highlight the importance of pre‐treating these nanowires under a reducing atmosphere to enhance their performance for CO oxidation. To explain these findings, we collected extended x‐ray adsorption fine structure (EXAFS) spectroscopy data, consistent with the presence of partial alloying with a tendency for Pt and Ni to segregate, thereby implying the formation of a Pt‐rich shell coupled with a Ni‐rich core. We also observed that the degree of alloying within the nanowires increased after annealing in a reducing atmosphere, a finding deduced through analysis of the coordination numbers and calculations of Cowley's short range order parameters.

 

As part of an effort to characterize clusters and intermediate phases likely to be encountered along solution reaction pathways that produce iron and aluminum oxide-hydroxides from Fe and Al precursors, the complete structure of Al10O14(OH)2 (akdalaite) was determined from a combination of single-crystal X-ray diffraction (SC-XRD) data collected at 100 K to define the Al and O positions, and solid-state nuclear magnetic resonance (NMR) and neutron powder diffraction (NPD) data collected at room temperature (~300 K) to precisely determine the nature of hydrogen in the structure. Two different synthesis routes produced different crystal morphologies. Using an aluminum oxyhydroxide floc made from mixing AlCl3 and 0.48 M NaOH, the product had uniform needle morphology, while using nanocrystalline boehmite (Vista Chemical Company Catapal D alumina) as the starting material produced hexagonal plates. Akdalaite crystallizes in the space group P63mc with lattice parameters of a = 5.6244(3) Å and c = 8.8417(3) Å (SC-XRD) and a = 5.57610(2) Å and c = 8.77247(6) Å (NPD). The crystal structure features Al13O40 Keggin clusters. The structural chemistry of akdalaite is nonideal but broadly conforms to that of ferrihydrite, the nanomineral with which it is isostructural.