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Field-induced reagent concentration and sulfur adsorption enable efficient electrocatalytic semihydrogenation of alkynes

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 semihydrogenatio...

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Autores principales: Gao, Ying, Yang, Rong, Wang, Changhong, Liu, Cuibo, Wu, Yongmeng, Li, Huizhi, Zhang, Bin
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Association for the Advancement of Science 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8865775/
https://www.ncbi.nlm.nih.gov/pubmed/35196082
http://dx.doi.org/10.1126/sciadv.abm9477
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author Gao, Ying
Yang, Rong
Wang, Changhong
Liu, Cuibo
Wu, Yongmeng
Li, Huizhi
Zhang, Bin
author_facet Gao, Ying
Yang, Rong
Wang, Changhong
Liu, Cuibo
Wu, Yongmeng
Li, Huizhi
Zhang, Bin
author_sort Gao, Ying
collection PubMed
description 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.
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spelling pubmed-88657752022-03-10 Field-induced reagent concentration and sulfur adsorption enable efficient electrocatalytic semihydrogenation of alkynes Gao, Ying Yang, Rong Wang, Changhong Liu, Cuibo Wu, Yongmeng Li, Huizhi Zhang, Bin Sci Adv Physical and Materials Sciences 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. American Association for the Advancement of Science 2022-02-23 /pmc/articles/PMC8865775/ /pubmed/35196082 http://dx.doi.org/10.1126/sciadv.abm9477 Text en Copyright © 2022 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC). https://creativecommons.org/licenses/by-nc/4.0/This is an open-access article distributed under the terms of the Creative Commons Attribution-NonCommercial license (https://creativecommons.org/licenses/by-nc/4.0/) , which permits use, distribution, and reproduction in any medium, so long as the resultant use is not for commercial advantage and provided the original work is properly cited.
spellingShingle Physical and Materials Sciences
Gao, Ying
Yang, Rong
Wang, Changhong
Liu, Cuibo
Wu, Yongmeng
Li, Huizhi
Zhang, Bin
Field-induced reagent concentration and sulfur adsorption enable efficient electrocatalytic semihydrogenation of alkynes
title Field-induced reagent concentration and sulfur adsorption enable efficient electrocatalytic semihydrogenation of alkynes
title_full Field-induced reagent concentration and sulfur adsorption enable efficient electrocatalytic semihydrogenation of alkynes
title_fullStr Field-induced reagent concentration and sulfur adsorption enable efficient electrocatalytic semihydrogenation of alkynes
title_full_unstemmed Field-induced reagent concentration and sulfur adsorption enable efficient electrocatalytic semihydrogenation of alkynes
title_short Field-induced reagent concentration and sulfur adsorption enable efficient electrocatalytic semihydrogenation of alkynes
title_sort field-induced reagent concentration and sulfur adsorption enable efficient electrocatalytic semihydrogenation of alkynes
topic Physical and Materials Sciences
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8865775/
https://www.ncbi.nlm.nih.gov/pubmed/35196082
http://dx.doi.org/10.1126/sciadv.abm9477
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