The semihydrogenation of alkynes into alkenes rather than alkanes is of great importance in the chemical industry. Unfortunately, state‐of‐the‐art heterogeneous catalysts hardly achieve high turnover frequencies (TOFs) simultaneously with almost full conversion, excellent selectivity, and good stability. Here, we used metal–organic frameworks (MOFs) containing Zr metal nodes (“UiO”) with tunable wettability and electron‐withdrawing ability as activity accelerators for the semihydrogenation of alkynes catalyzed by sandwiched palladium nanoparticles (Pd NPs). Impressively, the porous hydrophobic UiO support not only leads to an enrichment of phenylacetylene around the Pd NPs but also renders the Pd surfaces more electron‐deficient, which leads to a remarkable catalysis performance, including an exceptionally high TOF of 13835 h−1, 100 % phenylacetylene conversion 93.1 % selectivity towards styrene, and no activity decay after successive catalytic cycles. The strategy of using molecularly tailored supports is universal for boosting the selective semihydrogenation of various terminal and internal alkynes.

Metal-organic frameworks (MOFs) have great potential to become innovative heterogeneous supports for immobilizing catalytically active noble metal nanoparticles (NPs). However, unlike metal oxide supports, the interfacial interactions between noble metal NPs and MOFs are currently neglected, thus dramatically diminishing the advantage of MOFs as supports. Herein, ZIFs(Co/Zn)@M (M = Pd, Pt or Au) nanocomposites with well-defined interfaces are synthesized and used as catalysts in gas-phase CO oxidation and liquid-phase C6H5CHO oxidation. Notably, in both reactions, ZIF-67(Co)@M samples exhibit better catalytic activity than ZIF-8(Zn)@M samples, and moreover, the catalytic activity of ZIFs@Pd is higher than that of ZIFs@Pt and ZIFs@Au samples. Experimental and theoretical results reveal that the enhanced catalytic activity originates from the interfacial electron transfer from ZIFs to noble metal NPs as well as the coupling between d band of noble metal in NPs and metal node in ZIFs.

A series of mesoporous NiO–Y2O3–Al2O3 composite oxides with different yttrium contents were synthesized by either a one-pot evaporation-induced self-assembly (EISA) method or impregnation for carbon dioxide reforming of methane (CRM).