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Intermetallic PdZn nanoparticles catalyze the continuous-flow hydrogenation of alkynols to cis-enols

Designing highly active and stable lead-free palladium-based catalysts without introducing surfactants and stabilizers is vital for large-scale and high-efficiency manufacturing of cis-enols via continuous-flow semi-hydrogenation of alkynols. Herein, we report an intermetallic PdZn/ZnO catalyst, des...

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Autores principales: Chen, Xiao, Shi, Chuang, Wang, Xing-Bao, Li, Wen-Ying, Liang, Changhai
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9814770/
https://www.ncbi.nlm.nih.gov/pubmed/36697793
http://dx.doi.org/10.1038/s42004-021-00612-0
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author Chen, Xiao
Shi, Chuang
Wang, Xing-Bao
Li, Wen-Ying
Liang, Changhai
author_facet Chen, Xiao
Shi, Chuang
Wang, Xing-Bao
Li, Wen-Ying
Liang, Changhai
author_sort Chen, Xiao
collection PubMed
description Designing highly active and stable lead-free palladium-based catalysts without introducing surfactants and stabilizers is vital for large-scale and high-efficiency manufacturing of cis-enols via continuous-flow semi-hydrogenation of alkynols. Herein, we report an intermetallic PdZn/ZnO catalyst, designed by using the coupling strategy of strong electrostatic adsorption and reactive metal-support interaction, which can be used as a credible alternative to the commercial PdAg/Al(2)O(3) and Lindlar catalysts. Intermetallic PdZn nanoparticles with electron-poor active sites on a Pd/ZnO catalyst significantly boost the thermodynamic selectivity with respect to the mechanistic selectivity and therefore enhance the selectivity towards cis-enols. Based on in situ diffuse reflectance infrared Fourier-transform spectra as well as simulations, we identify that the preferential adsorption of alkynol over enol on PdZn nanoparticles suppresses the over-hydrogenation of enols. These results suggest the application of fine surface engineering technology in oxide-supported metal (particles) could tune the ensemble and ligand effects of metallic active sites and achieve directional hydrogenation in fine chemical synthesis.
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spelling pubmed-98147702023-01-10 Intermetallic PdZn nanoparticles catalyze the continuous-flow hydrogenation of alkynols to cis-enols Chen, Xiao Shi, Chuang Wang, Xing-Bao Li, Wen-Ying Liang, Changhai Commun Chem Article Designing highly active and stable lead-free palladium-based catalysts without introducing surfactants and stabilizers is vital for large-scale and high-efficiency manufacturing of cis-enols via continuous-flow semi-hydrogenation of alkynols. Herein, we report an intermetallic PdZn/ZnO catalyst, designed by using the coupling strategy of strong electrostatic adsorption and reactive metal-support interaction, which can be used as a credible alternative to the commercial PdAg/Al(2)O(3) and Lindlar catalysts. Intermetallic PdZn nanoparticles with electron-poor active sites on a Pd/ZnO catalyst significantly boost the thermodynamic selectivity with respect to the mechanistic selectivity and therefore enhance the selectivity towards cis-enols. Based on in situ diffuse reflectance infrared Fourier-transform spectra as well as simulations, we identify that the preferential adsorption of alkynol over enol on PdZn nanoparticles suppresses the over-hydrogenation of enols. These results suggest the application of fine surface engineering technology in oxide-supported metal (particles) could tune the ensemble and ligand effects of metallic active sites and achieve directional hydrogenation in fine chemical synthesis. Nature Publishing Group UK 2021-12-13 /pmc/articles/PMC9814770/ /pubmed/36697793 http://dx.doi.org/10.1038/s42004-021-00612-0 Text en © The Author(s) 2021 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
Chen, Xiao
Shi, Chuang
Wang, Xing-Bao
Li, Wen-Ying
Liang, Changhai
Intermetallic PdZn nanoparticles catalyze the continuous-flow hydrogenation of alkynols to cis-enols
title Intermetallic PdZn nanoparticles catalyze the continuous-flow hydrogenation of alkynols to cis-enols
title_full Intermetallic PdZn nanoparticles catalyze the continuous-flow hydrogenation of alkynols to cis-enols
title_fullStr Intermetallic PdZn nanoparticles catalyze the continuous-flow hydrogenation of alkynols to cis-enols
title_full_unstemmed Intermetallic PdZn nanoparticles catalyze the continuous-flow hydrogenation of alkynols to cis-enols
title_short Intermetallic PdZn nanoparticles catalyze the continuous-flow hydrogenation of alkynols to cis-enols
title_sort intermetallic pdzn nanoparticles catalyze the continuous-flow hydrogenation of alkynols to cis-enols
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9814770/
https://www.ncbi.nlm.nih.gov/pubmed/36697793
http://dx.doi.org/10.1038/s42004-021-00612-0
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