In the field of renewable energy, the splitting of water into hydrogen and oxygen fuel gases using water electrolysis is a prominent topic. Traditionally, these catalytic processes have been performed by platinum‐group metal catalysts, which are effective at promoting water electrolysis but expensive and rare. The search for an inexpensive and Earth‐abundant catalyst has led to the development of 3d‐transition‐metal phosphides for the hydrogen evolution reaction. These catalysts have shown excellent activity and stability. In this review, we discuss the electronic and crystal structures of bulk and surface of selected Fe, Co, and Ni phosphides, and their relationships to the experimental catalytic activity. The various synthetic protocols towards the state‐of‐the‐art transition metal phosphide electrocatalysts are also discussed.

The effect of the crystal structure of ordered transition-metal phosphide catalysts on the hydrogen-evolution reaction is investigated using single crystals of iron-phosphide (FeP) and monoclinic nickel-diphosphide (m-NiP₂).

Herein, we describe the synthesis of a toroidal Au₁₀ cluster stabilized by N-heterocyclic carbene and halide ligands via reduction of the corresponding NHC–Au–X complexes (X = Cl, Br, I). The significant effect of the halide ligands on the formation, stability, and further conversions of these clusters is presented. While solutions of the chloride derivatives of Au₁₀ show no change even upon heating, the bromide derivative readily undergoes conversion to form a biicosahedral Au₂₅ cluster at room temperature. For the iodide derivative, the formation of a significant amount of Au₂₅ was observed even upon the reduction of NHC–Au–I. The isolated bromide derivative of the Au₂₅ cluster displays a relatively high (ca. 15%) photoluminescence quantum yield, attributed to the high rigidity of the cluster, which is enforced by multiple CH−π interactions within the molecular structure. Density functional theory computations are used to characterize the electronic structure and optical absorption of the Au₁₀ cluster. ¹³C-Labeling is employed to assist with characterization of the products and to observe their conversions by NMR spectroscopy.