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Tuning the selectivity of catalytic nitriles hydrogenation by structure regulation in atomically dispersed Pd catalysts

The product selectivity in catalytic hydrogenation of nitriles is strongly correlated with the structure of the catalyst. In this work, two types of atomically dispersed Pd species stabilized on the defect-rich nanodiamond-graphene (ND@G) hybrid support: single Pd atoms (Pd(1)/ND@G) and fully expose...

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Autores principales: Liu, Zhibo, Huang, Fei, Peng, Mi, Chen, Yunlei, Cai, Xiangbin, Wang, Linlin, Hu, Zenan, Wen, Xiaodong, Wang, Ning, Xiao, Dequan, Jiang, Hong, Sun, Hongbin, Liu, Hongyang, Ma, Ding
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8548558/
https://www.ncbi.nlm.nih.gov/pubmed/34702832
http://dx.doi.org/10.1038/s41467-021-26542-y
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author Liu, Zhibo
Huang, Fei
Peng, Mi
Chen, Yunlei
Cai, Xiangbin
Wang, Linlin
Hu, Zenan
Wen, Xiaodong
Wang, Ning
Xiao, Dequan
Jiang, Hong
Sun, Hongbin
Liu, Hongyang
Ma, Ding
author_facet Liu, Zhibo
Huang, Fei
Peng, Mi
Chen, Yunlei
Cai, Xiangbin
Wang, Linlin
Hu, Zenan
Wen, Xiaodong
Wang, Ning
Xiao, Dequan
Jiang, Hong
Sun, Hongbin
Liu, Hongyang
Ma, Ding
author_sort Liu, Zhibo
collection PubMed
description The product selectivity in catalytic hydrogenation of nitriles is strongly correlated with the structure of the catalyst. In this work, two types of atomically dispersed Pd species stabilized on the defect-rich nanodiamond-graphene (ND@G) hybrid support: single Pd atoms (Pd(1)/ND@G) and fully exposed Pd clusters with average three Pd atoms (Pd(n)/ND@G), were fabricated. The two catalysts show distinct difference in the catalytic transfer hydrogenation of nitriles. The Pd(1)/ND@G catalyst preferentially generates secondary amines (Turnover frequency (TOF@333 K 709 h(−1), selectivity >98%), while the Pd(n)/ND@G catalyst exhibits high selectivity towards primary amines (TOF@313 K 543 h(−1), selectivity >98%) under mild reaction conditions. Detailed characterizations and density functional theory (DFT) calculations show that the structure of atomically dispersed Pd catalysts governs the dissociative adsorption pattern of H(2) and also the hydrogenation pathway of the benzylideneimine (BI) intermediate, resulting in different product selectivity over Pd(1)/ND@G and Pd(n)/ND@G, respectively. The structure-performance relationship established over atomically dispersed Pd catalysts provides valuable insights for designing catalysts with tunable selectivity.
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spelling pubmed-85485582021-10-29 Tuning the selectivity of catalytic nitriles hydrogenation by structure regulation in atomically dispersed Pd catalysts Liu, Zhibo Huang, Fei Peng, Mi Chen, Yunlei Cai, Xiangbin Wang, Linlin Hu, Zenan Wen, Xiaodong Wang, Ning Xiao, Dequan Jiang, Hong Sun, Hongbin Liu, Hongyang Ma, Ding Nat Commun Article The product selectivity in catalytic hydrogenation of nitriles is strongly correlated with the structure of the catalyst. In this work, two types of atomically dispersed Pd species stabilized on the defect-rich nanodiamond-graphene (ND@G) hybrid support: single Pd atoms (Pd(1)/ND@G) and fully exposed Pd clusters with average three Pd atoms (Pd(n)/ND@G), were fabricated. The two catalysts show distinct difference in the catalytic transfer hydrogenation of nitriles. The Pd(1)/ND@G catalyst preferentially generates secondary amines (Turnover frequency (TOF@333 K 709 h(−1), selectivity >98%), while the Pd(n)/ND@G catalyst exhibits high selectivity towards primary amines (TOF@313 K 543 h(−1), selectivity >98%) under mild reaction conditions. Detailed characterizations and density functional theory (DFT) calculations show that the structure of atomically dispersed Pd catalysts governs the dissociative adsorption pattern of H(2) and also the hydrogenation pathway of the benzylideneimine (BI) intermediate, resulting in different product selectivity over Pd(1)/ND@G and Pd(n)/ND@G, respectively. The structure-performance relationship established over atomically dispersed Pd catalysts provides valuable insights for designing catalysts with tunable selectivity. Nature Publishing Group UK 2021-10-26 /pmc/articles/PMC8548558/ /pubmed/34702832 http://dx.doi.org/10.1038/s41467-021-26542-y 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
Liu, Zhibo
Huang, Fei
Peng, Mi
Chen, Yunlei
Cai, Xiangbin
Wang, Linlin
Hu, Zenan
Wen, Xiaodong
Wang, Ning
Xiao, Dequan
Jiang, Hong
Sun, Hongbin
Liu, Hongyang
Ma, Ding
Tuning the selectivity of catalytic nitriles hydrogenation by structure regulation in atomically dispersed Pd catalysts
title Tuning the selectivity of catalytic nitriles hydrogenation by structure regulation in atomically dispersed Pd catalysts
title_full Tuning the selectivity of catalytic nitriles hydrogenation by structure regulation in atomically dispersed Pd catalysts
title_fullStr Tuning the selectivity of catalytic nitriles hydrogenation by structure regulation in atomically dispersed Pd catalysts
title_full_unstemmed Tuning the selectivity of catalytic nitriles hydrogenation by structure regulation in atomically dispersed Pd catalysts
title_short Tuning the selectivity of catalytic nitriles hydrogenation by structure regulation in atomically dispersed Pd catalysts
title_sort tuning the selectivity of catalytic nitriles hydrogenation by structure regulation in atomically dispersed pd catalysts
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8548558/
https://www.ncbi.nlm.nih.gov/pubmed/34702832
http://dx.doi.org/10.1038/s41467-021-26542-y
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