Selective semi-hydrogenation of alkynes is a significant reaction for preparing functionalized alkenes. Electrochemical semi-hydrogenation presents a sustainable alternative to the traditional thermal process. In this research, affordable copper acetylacetonate is employed as a catalyst precursor for the electrocatalytic hydrogenation of alkynes, using MeOH as the hydrogen source in an undivided cell. Good to excellent yields for both aromatic and aliphatic internal/terminal alkynes are obtained under constant current conditions. Notably, up to 99% Z selectivity is achieved for various internal alkynes. Mechanistic investigations revealed the formation of copper nanoparticles (NPs) at the cathode during electrolysis, acting as the catalyst for the selective semireduction of alkynes. The copper NPs deposited cathode demonstrated reusable for further hydrogenation.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1002/smll.202401107 | DOI Listing |
Angew Chem Int Ed Engl
January 2025
Key Laboratory of Green Chemistry and Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064, China.
Electrocatalytic transfer alkyne semi-hydrogenation with HO as hydrogen source is industrially promising for selective electrosynthesis of high value-added alkenes while inhibiting byproduct alkanes. Although great achievements, their development has remarkably restricted by designing atomically sophisticated electrocatalysts. Here, we reported single-crystalline mesoporous copper nanoplates (meso-Cu PLs) as a robust yet highly efficient electrocatalyst for selective alkene electrosynthesis from transfer semi-hydrogenation reaction of alkyne in HO.
View Article and Find Full Text PDFMater Horiz
January 2025
School of Materials Science and Engineering, National Institute for Advanced Materials, Nankai University, Tianjin, 300350, China.
The semi-hydrogenation of alkynes into alkenes rather than alkanes is of great importance in the chemical industry, and palladium-based metallic catalysts are currently employed. Unfortunately, a fairly high cost and uncontrollable over-hydrogenation impeded the application of Pd-based catalysts on a large scale. Herein, a sandwich structure single atom Pd catalyst, Z@Pd@Z, was prepared impregnation exchange and epitaxial growth methods (Z stands for ZIF-8), in which Pd single atoms were stabilized by pyrrolic N in a zeolitic imidazolate framework (ZIF-8).
View Article and Find Full Text PDFSmall
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 PDFInorg Chem Front
December 2024
Department of Chemistry, University of Manchester Manchester M13 9PL UK
Phenylacetylene is a detrimental impurity in the polymerisation of styrene, capable of poisoning catalysts even at ppm levels and significantly degrading the quality of polystyrene. The semi-hydrogenation of phenylacetylene to styrene instead of ethylbenzene is, therefore, an important industrial process. We report a novel cerium(iv)-based metal-organic framework (denoted as Ce-bptc), which comprises {Ce} clusters bridged by biphenyl-3,3',5,5'-tetracarboxylate linkers.
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 PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!