Pd nanoparticles embedded in MoC were successfully prepared from a high-temperature pulse, and are efficient for semi-hydrogenation of alkynes to alkenes, where the embedded Pd sites possessed appropriate alkyne adsorption but suppressed alkene adsorption, thus exhibiting both high activities and good alkene selectivities in the hydrogenation of various alkynes.
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http://dx.doi.org/10.1039/d4cc04498c | DOI Listing |
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December 2024
School of Chemistry, Dalian University of Technology, Dalian, 116024, China.
Confinement of metal species in porous supports is an effective strategy to optimize hydrogenation performance ascribing to tunable nanopore environments. However, only focusing on the electronic structure modulation for metal species has limited the design of improved catalysts. Herein, spatial confinement strategy is reported for constructing ultrasmall metal clusters in nitro-bonded COF (M@TpPa-NO, M = Pd, Pt, Ru, Rh, Ir).
View Article and Find Full Text PDFJ Org Chem
December 2024
Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan.
Using amines in catalytic transfer hydrogenation (TH) is challenging, despite their potential availability as a hydrogen source. Here, we describe a photoredox/nickel-catalyzed TH of alkyne through an intermediary aminoalkyl Ni species. This reaction successfully provided functionalized ()-alkenes, such as (homo)allyl ethers, alcohols, and amides (/ = up to >99:1), and the reaction thus bypasses a limitation of substrate scope in TH using amine and a Lindlar catalyst.
View Article and Find Full Text PDFChem Commun (Camb)
December 2024
Beijing Advanced Innovation Center for Soft Matter, Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China.
Pd nanoparticles embedded in MoC were successfully prepared from a high-temperature pulse, and are efficient for semi-hydrogenation of alkynes to alkenes, where the embedded Pd sites possessed appropriate alkyne adsorption but suppressed alkene adsorption, thus exhibiting both high activities and good alkene selectivities in the hydrogenation of various alkynes.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, 210093, China.
An enzyme-mimicking catalytic system has been established using a singular palladium-based octahedral cage as the supramolecular reactor, deftly unlocking the off-on-off selectivity in the semi-hydrogenation of alkynes. Water serves as a critical regulator, modulating the catalyst states, reaction rates, and endpoints. The choice of solvent system influences the activity of host-guest binding and the reaction types of homogeneous and heterogeneous catalysis, effectively modifying the reaction steps involved in the Z→E isomerization during the semi-hydrogenation of alkynes.
View Article and Find Full Text PDFPrecis Chem
May 2024
New Cornerstone Science Laboratory, State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, and National & Local Joint Engineering Research Center of Preparation Technology of Nanomaterials, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
Surface modification of metallic nanocatalysts with organic ligands has emerged as an effective strategy to enhance catalytic selectivity, although often at the expense of catalytic activity. In this study, we demonstrate a compelling approach by surface modifying PdS nanocrystals with PPh ligands, resulting in a catalyst with excellent catalytic activity and durable selectivity for the semi-hydrogenation of terminal alkynes. Experimental and theoretical investigations reveal that the presence of S sites on the Pd surface directs PPh ligands to preferentially form covalent bonds with S, creating distinctive surface S=PPh motifs.
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