Efficient electrocatalytic alkyne semihydrogenation with potential/time-independent selectivity and Faradaic efficiency (FE) is vital for industrial alkene productions. Here, sulfur-tuned effects and field-induced reagent concentration are proposed to promote electrocatalytic alkyne semihydrogenation. Density functional theory calculations reveal that bulk sulfur anions intrinsically weaken alkene adsorption, and surface thiolates lower the activation energy of water and the Gibbs free energy for H* formation. The finite element method shows high-curvature structured catalyst concentrates K + by enhancing electric field at the tips, accelerating more H* formation from water electrolysis via sulfur anion–hydrated cation networks, and promoting alkyne transformations. So, self-supported Pd nanotips with sulfur modifiers are developed for electrochemical alkyne semihydrogenation with up to 97% conversion yield, 96% selectivity, 75% FE, and a reaction rate of 465.6 mmol m −2 hour −1 . Wide potential window and time irrelevance for high alkene selectivity, good universality, and easy access to deuterated alkenes highlight the promising potential.

Room temperature and selective hydrogenation of quinolines to 1,2,3,4-tetrahydroquinolines using a safe and clean hydrogen donor catalyzed by cost-effective materials is significant yet challenging because of the difficult activation of quinolines and H2. Here, a fluorine-modified cobalt catalyst is synthesized via electroreduction of a Co(OH)F precursor that exhibits high activity for electrocatalytic hydrogenation of quinolines by using H2O as the hydrogen source to produce 1,2,3,4-tetrahydroquinolines with up to 99% selectivity and 94% isolated yield under ambient conditions. Fluorine surface-sites are shown to enhance the adsorption of quinolines and promote water activation to produce active atomic hydrogen (H*) by forming F−-K+(H2O)7 networks. A 1,4/2,3-addition pathway involving H* is proposed through combining experimental and theoretical results. Wide substrate scopes, scalable synthesis of bioactive precursors, facile preparation of deuterated analogues, and the paired synthesis of 1,2,3,4-tetrahydroquinoline and industrially important adiponitrile at a low voltage highlight the promising applications of this methodology.

Developing a step-economical approach for efficient synthesis of α,β-deuterio aryl ethylamines (α,β-DAEAs) with high deuterium ratios using an easy-to-handle deuterated source under ambient conditions is highly desirable. Here we report a room-temperature one-pot two-step transformation of aryl acetonitriles to α,β-DAEAs with up to 92% isolated yield and 99% α,β-deuterium ratios using D2O as a deuterium source. The process involves a fast α-C − H/C − D exchange and tandem electroreductive deuteration of C ≡ N over an in situ formed low-coordinated Fe nanoparticle cathode. The moderate adsorptions of nitriles/imine intermediates and the promoted formation of active hydrogen (H*) on unsaturated Fe sites facilitate the electroreduction process. In situ Raman confirms co-adsorption of aryl rings and the C ≡ N group on the Fe surface. A proposed H*-addition pathway is confirmed by the detected hydrogen and carbon radicals. Wide substrate scope, parallel synthesis of multiple α,β-DAEAs, and successful preparation of α,β-deuterated Melatonin and Komavine highlight the potential.