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Uniform single atomic Cu(1)-C(4) sites anchored in graphdiyne for hydroxylation of benzene to phenol
For single-atom catalysts (SACs), the catalyst supports are not only anchors for single atoms, but also modulators for geometric and electronic structures, which determine their catalytic performance. Selecting an appropriate support to prepare SACs with uniform coordination environments is critical...
Autores principales: | , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Oxford University Press
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9584062/ https://www.ncbi.nlm.nih.gov/pubmed/36285293 http://dx.doi.org/10.1093/nsr/nwac018 |
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author | Yu, Jia Cao, Changyan Jin, Hongqiang Chen, Weiming Shen, Qikai Li, Peipei Zheng, Lirong He, Feng Song, Weiguo Li, Yuliang |
author_facet | Yu, Jia Cao, Changyan Jin, Hongqiang Chen, Weiming Shen, Qikai Li, Peipei Zheng, Lirong He, Feng Song, Weiguo Li, Yuliang |
author_sort | Yu, Jia |
collection | PubMed |
description | For single-atom catalysts (SACs), the catalyst supports are not only anchors for single atoms, but also modulators for geometric and electronic structures, which determine their catalytic performance. Selecting an appropriate support to prepare SACs with uniform coordination environments is critical for achieving optimal performance and clarifying the relationship between the structure and the property of SACs. Approaching such a goal is still a significant challenge. Taking advantage of the strong d-π interaction between Cu atoms and diacetylenic in a graphdiyne (GDY) support, we present an efficient and simple strategy for fabricating Cu single atoms anchored on GDY (Cu(1)/GDY) with uniform Cu(1)-C(4) single sites under mild conditions. The Cu atomic structure was confirmed by combining synchrotron radiation X-ray absorption spectroscopy, X-ray photoelectron spectroscopy and density functional theory (DFT) calculations. The as-prepared Cu(1)/GDY exhibits much higher activity than state-of-the-art SACs in direct benzene oxidation to phenol with H(2)O(2) reaction, with turnover frequency values of 251 h(−1) at room temperature and 1889 h(−1) at 60°C, respectively. Furthermore, even with a high benzene conversion of 86%, high phenol selectivity (96%) is maintained, which can be ascribed to the hydrophobic and oleophyllic surface nature of Cu(1)/GDY for benzene adsorption and phenol desorption. Both experiments and DFT calculations indicate that Cu(1)-C(4) single sites are more effective at activating H(2)O(2) to form Cu=O bonds, which are important active intermediates for benzene oxidation to phenol. |
format | Online Article Text |
id | pubmed-9584062 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | Oxford University Press |
record_format | MEDLINE/PubMed |
spelling | pubmed-95840622022-10-24 Uniform single atomic Cu(1)-C(4) sites anchored in graphdiyne for hydroxylation of benzene to phenol Yu, Jia Cao, Changyan Jin, Hongqiang Chen, Weiming Shen, Qikai Li, Peipei Zheng, Lirong He, Feng Song, Weiguo Li, Yuliang Natl Sci Rev Research Article For single-atom catalysts (SACs), the catalyst supports are not only anchors for single atoms, but also modulators for geometric and electronic structures, which determine their catalytic performance. Selecting an appropriate support to prepare SACs with uniform coordination environments is critical for achieving optimal performance and clarifying the relationship between the structure and the property of SACs. Approaching such a goal is still a significant challenge. Taking advantage of the strong d-π interaction between Cu atoms and diacetylenic in a graphdiyne (GDY) support, we present an efficient and simple strategy for fabricating Cu single atoms anchored on GDY (Cu(1)/GDY) with uniform Cu(1)-C(4) single sites under mild conditions. The Cu atomic structure was confirmed by combining synchrotron radiation X-ray absorption spectroscopy, X-ray photoelectron spectroscopy and density functional theory (DFT) calculations. The as-prepared Cu(1)/GDY exhibits much higher activity than state-of-the-art SACs in direct benzene oxidation to phenol with H(2)O(2) reaction, with turnover frequency values of 251 h(−1) at room temperature and 1889 h(−1) at 60°C, respectively. Furthermore, even with a high benzene conversion of 86%, high phenol selectivity (96%) is maintained, which can be ascribed to the hydrophobic and oleophyllic surface nature of Cu(1)/GDY for benzene adsorption and phenol desorption. Both experiments and DFT calculations indicate that Cu(1)-C(4) single sites are more effective at activating H(2)O(2) to form Cu=O bonds, which are important active intermediates for benzene oxidation to phenol. Oxford University Press 2022-02-11 /pmc/articles/PMC9584062/ /pubmed/36285293 http://dx.doi.org/10.1093/nsr/nwac018 Text en © The Author(s) 2022. Published by Oxford University Press on behalf of China Science Publishing & Media Ltd. https://creativecommons.org/licenses/by/4.0/This is an Open Access article distributed under the terms of the Creative Commons Attribution License (https://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse, distribution, and reproduction in any medium, provided the original work is properly cited. |
spellingShingle | Research Article Yu, Jia Cao, Changyan Jin, Hongqiang Chen, Weiming Shen, Qikai Li, Peipei Zheng, Lirong He, Feng Song, Weiguo Li, Yuliang Uniform single atomic Cu(1)-C(4) sites anchored in graphdiyne for hydroxylation of benzene to phenol |
title | Uniform single atomic Cu(1)-C(4) sites anchored in graphdiyne for hydroxylation of benzene to phenol |
title_full | Uniform single atomic Cu(1)-C(4) sites anchored in graphdiyne for hydroxylation of benzene to phenol |
title_fullStr | Uniform single atomic Cu(1)-C(4) sites anchored in graphdiyne for hydroxylation of benzene to phenol |
title_full_unstemmed | Uniform single atomic Cu(1)-C(4) sites anchored in graphdiyne for hydroxylation of benzene to phenol |
title_short | Uniform single atomic Cu(1)-C(4) sites anchored in graphdiyne for hydroxylation of benzene to phenol |
title_sort | uniform single atomic cu(1)-c(4) sites anchored in graphdiyne for hydroxylation of benzene to phenol |
topic | Research Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9584062/ https://www.ncbi.nlm.nih.gov/pubmed/36285293 http://dx.doi.org/10.1093/nsr/nwac018 |
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