Olefin hydrogenation under mild condition is crucial and challenging for industrial applications. Herein, defective UiO-66(Ce) was constructed by using cyanuric acid as the molecular etching “scissors” and further to synthesize heterogeneous catalyst with highly dispersed RuNi nanoparticles (Ru₁Ni_1.5@UiO-66(Ce)-12 h). The construction of Ce-O-Ru/Ni heterogeneous interfaces and Ni–Ru bonds provide electron transfer channels from Ce-oxo clusters and Ni species to Ru species. Furthermore, the microenvironment and electronic structure of Ru⁰ active sites were synergistically regulated by adjusting the content of metal-organic frameworks (MOFs) defects and Ni promoter, thereby enhancing the adsorption and activation ability of H–H and C=C bonds. Therefore, Ru₁Ni_1.5@UiO-66(Ce)-12 h achieved dicyclopentadiene saturated hydrogenation (100% conversion) to tetrahydrodicyclopentadiene (~ 100% selectivity) under mild condition (35 °C, 1 MPa) with only 25 min. Meanwhile, the sample exhibited excellent structural stability after 6 cycles test. This study provides a promising strategy for the rational design of remarkable noble metal-based catalysts for practical applications.

Efficient hydrogen production via photocatalysis with high utilization efficiency of Pt cocatalyst is of great importance for sustainable development. In this work, we report an in situ auto-reduction strategy to encapsulate highly dispersed Pt clusters inside the cages of MIL-125-NH₂. The amino groups in MIL-125-NH₂ first react with formaldehyde to form reducing groups (i.e., –NH-CH₂OH), which can in situ auto-reduce the confined Pt²⁺ ions to ultrasmall Pt clusters within the cavities. With optimized Pt content, photocatalytic H₂ production over the obtained Pt(1.5)/MIL-125-NH-CH₂OH catalyst with 1.43 wt.% Pt loading achieved as high as 4, 496.4 µmol·g⁻¹·h⁻¹ under visible light (λ > 420 nm) due to the facilitated transfer and separation of the photo-induced charger carriers arising from the synergetic effects between highly dispersed Pt clusters and MIL-125-NH-CH₂OH framework. This in situ auto-reduction strategy may be extended to encapsulate various kinds of metal or alloy clusters/nanoparticles within amino-functioned metal-organic frameworks (MOFs) with superior properties and excellent performance.