Noble‐metal catalysts serve as an irreplaceable role in pharmaceutical, perfume and fine chemicals fields. However, there still remains a grand challenge in controlling chemoselectivity. Herein, we have synthesized a bimetallic nanostructure supported on porous metal‐organic frameworks (Pt−Fe/UiO‐66, Pt‐Ni3/UiO‐66), in which Pt nanoparticles was modified with non‐noble metal (Fe or Ni) directly. The as‐synthesized catalysts can function as a switch for selective hydrogenation of α,β‐unsaturated aldehydes to afford the potential products on‐demand. In comparison with the conventional Pt‐based catalysts, Pt−Fe/UiO‐66 and Pt‐Ni3/UiO‐66 catalysts exhibit excellently catalytic activity, enhanced selectivity and improved stability for selectivity hydrogenation. The partial charge reconfiguration and electronic coupling effect existing in such distinctive bicomponent nanocatalysts was confirmed by some comprehensive characterization and density functional theory (DFT) calculations. The developed method for precisely modification the composition and interaction between the noble metal and non‐noble metal provides a feasible avenue to design the advanced catalysts.

The construction of low-cost electrocatalysts with good conductivity, excellent intrinsic activity, and superior stability is crucial for the hydrogen evolution reaction (HER). Herein, we report an outstanding catalyst (Ni 0.2 Mo 0.8 N/NiMoP 2 /MoO 2 @ NC) consisting of NiMo-based nanorod arrays supported on Ni foams for the efficient alkaline HER. It shows an ultralow overpotential of 48 mV and remarkable longevity for over 145 h at 10 mA cm −2 in 1.0 M KOH. The integration of ample compositions is favorable to the formation of heterointerfaces, accelerating electron transfer. The assembly of transition metal nitrides and phosphides fully develops the electrical conductivity of metal materials, which paves the way for superstability. The superior electrocatalytic activities can be attributed to the vital features, including the synergistic effect of Ni 0.2 Mo 0.8 N and NiMoP 2 , good electrical conductivity of MoO 2 , and corrosion resistance of NC basement. The present work proposes that regulating compositions and hierarchical nanostructures are of significance in developing electrode materials for the HER.