The fabrication of low-cost and earth-abundant electrocatalysts for the hydrogen evolution reaction (HER) over a broad pH range is attractive. In this work, a facile precursor route is developed to synthesize flower-like nickel phosphide microballs with a diameter of approximately 12 μm. With a controlled phosphorization temperature, flower-like nickel phosphide microballs with different crystalline structures (Ni P and Ni P) were obtained easily. Flower-like Ni P microballs possessed two advantageous features for enhanced HER: fast vectorial electron transfer path along the building block nanoplates and enhanced inherent catalytic activity of each active site for high-energy (0 0 1) facets. The flower-like Ni P microballs electrocatalyst thus displayed excellent activity for the HER with a low overpotential (η) of 35.4 mV to reach current densities of 10 mA cm and a small Tafel slope of 48 mV dec in acid solution. In addition, it showed excellent activity in 1 m KOH with η=47 mV at 10 mA cm . DFT studies indicated that the free energy of hydrogen adsorbed on the Ni site of Ni P was 0.152 eV, which is smaller than that of the Ni site of Ni P (0.182 eV). Therefore, flower-like Ni P microballs exhibited better HER activity than Ni P, which is consistent with our HER data. This hierarchical structure with exposed high-energy (0 0 1) facets paves the way to design and synthesize low-cost, high-performance catalysts for the HER.

Cooperatively bimetallic organic catalysis, coupling actions of two metal centers in a catalytic organic transformation via co‐activation of a single molecule or synergistic activation of two molecules, has witnessed rapid development in the last decades. This cooperative reacting mode creates new catalytic platforms to facilitate the characterization of bimetallic reaction pathways, offers remarkable improvements to some well‐established reactions, or exhibit unprecedented reactivity. Herein, we demonstrate perspectives of some significant contributions in the field of cooperatively bimetallic organic catalysis using dinucleating complexes with late transition metals. Based on different activation modes for the catalysis, the major advances are classified into: (1) bimetallic co‐activation of small molecules; (2) bimetallic co‐activation of single molecules; (3) bimetallic dual‐activation of two molecules. The mechanisms are also discussed to facilitate the understanding of the way of the metal‐metal cooperation involved in the catalytic cycles.

We report a general photocatalytic protocol for the remote C(sp 3 )−H bond amination of free aliphatic alcohols. The electron transfer between the abundant and inexpensive catalyst FeCl 3 and simple alkanols under blue LED irradiation enables the alkoxy radical formation under mild redox-neutral conditions, with no need for additional oxidant and prefunctionalization. The subsequent selective 1,5-hydrogen atom transfer (HAT) and amination provide a simple and efficient way to access molecular complexity from readily available and bulk alcohols.

We report a photoinduced iron/copper dual-catalytic strategy for the radical decarboxylation functionalization of aliphatic carboxylic acids. The photoinduced ligand-to-iron charge transfer process under light was initially occurred to generate an unstabilized alkyl radical, and the copper catalyst delivered the radical and enabled the subsequent coupling reactions to form C–N or C–C bonds. By merging iron-catalyzed decarboxylation with copper catalysis, this system allows the smooth conversion of a wide range of aliphatic carboxylic acids for the amination, decarboxylative dehydrogenation, and alkylation efficiently. A wide variety of complex drug or natural molecules is applicable, suggesting that this strategy would facilitate rapid compound library synthesis and benefit to the discovery of pharmaceutical agents.

The selective α-C−C bond cleavage of unfunctionalized secondary (2°) and tertiary alcohols (3°) is essential for valorization of macromolecules and biopolymers. We developed a blue-light-driven iron catalysis for aerobic oxidation of 2°and 3°alcohols to acids via α-C−C bond cleavages at room temperature. The first example of oxygenation of the simple tertiary alcohols was reported. The iron catalyst and blue light play critical roles to enable the formation of highly reactive O radicals from alcohols and the consequent two α-C−C bond cleavages.Letter pubs.acs.org/OrgLett