|
|||||
|
|
Selective Transfer Semihydrogenation of Alkynes with H2O (D2O) as the H (D) Source over a Pd-P Cathode |
|
| Authors: | Yongmeng Wu Dr Cuibo Liu Dr Changhong Wang Dr Siyu Lu Prof Bin Zhang |
| Institution: | 1. Institute of Molecular Plus, Department of Chemistry, School of Science, Tianjin University, Tianjin, 300072 China
These authors contributed equally to this work.;2. Institute of Molecular Plus, Department of Chemistry, School of Science, Tianjin University, Tianjin, 300072 China;3. Green Catalysis Center, College of Chemistry, Zhengzhou University, Zhengzhou, 450000 China |
| Abstract: | We reported a selective semihydrogenation (deuteration) of numerous terminal and internal alkynes using H2O (D2O) as the H (D) source over a Pd-P alloy cathode at a lower potential. P-doping caused the enhanced specific adsorption of alkynes and the promoted intrinsic activity for producing adsorbed atomic hydrogen (H*ads) from water electrolysis. The semihydrogenation of alkynes could be accomplished at a lower potential with up to 99 % selectivity and 78 % Faraday efficiency of alkene products, outperforming pure Pd and commercial Pd/C. This electrochemical semihydrogenation of alkynes might proceed via a H*ads addition pathway rather than a proton-coupled electron transfer process. The decreased amount of H*ads at a lower potential and the more preferential adsorption of the Pd-P to C≡C π bond than C=C moiety resulted in the excellent alkene selectivity. This method was capable of producing mono-, di-, and tri-deuterated alkenes with up to 99 % deuterium incorporation. |
| Keywords: | alkynes deuteration electrocatalysis Pd-P nanostructures semihydrogenation |