Novel Ni–Co–P hollow nanobricks are constructed with oriented nanosheets and manifest as an excellent bifunctional electrocatalyst for overall water splitting.

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Precise control of alloying sites has long been a challenging pursuit, yet little has been achieved for the atomic-level manipulation of metallic nanomaterials. Here we describe utilization of a surface motif exchange (SME) reaction to selectively replace the surface motifs of parent [Ag44(SR)30]4− (SR = thiolate) nanoparticles (NPs), leading to bimetallic NPs with well-defined molecular formula and atomically-controlled alloying sites in protecting shell. A systematic mass (and tandem mass) spectrometry analysis suggests that the SME reaction is an atomically precise displacement of SR–Ag(I)–SR-protecting modules of Ag NPs by the incoming SR–Au(I)–SR modules, giving rise to a core-shell [Ag32@Au12(SR)30]4−. Theoretical calculation suggests that the thermodynamically less favorable core-shell Ag@Au nanostructure is kinetically stabilized by the intermediate Ag20 shell, preventing inward diffusion of the surface Au atoms. The delicate SME reaction opens a door to precisely control the alloying sites in the protecting shell of bimetallic NPs with broad utility.

We demonstrate the use of selective electrocatalysts to run a direct methanol fuel cell at high concentrations of methanol.

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In this work, the effects of thiolate ligands (-SR, e.g., chain length and functional moiety) on the accessibility and catalytic activity of thiolate-protected gold nanoclusters (e.g., Au (SR) ) for 4-nitrophenol hydrogenation is reported. The data suggest that Au (SR) bearing a shorter alkyl chain shows a better accessibility to the substrates (shown by shorter induction time, t ) and a higher catalytic activity (shown by higher apparent reaction rate constant, k ). The functional moiety of the ligands is another determinant factor, which clearly suggests that ligand engineering of Au (SR) would be an efficient platform for fine-tuning its catalytic properties.

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