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Title: Zero-Valent Palladium Single-Atoms Catalysts Confined in Black Phosphorus for Efficient Semi-Hydrogenation

Abstract

Single-atom catalysts (SACs) represent a new frontier in heterogeneous catalysis due to their remarkable catalytic properties and maximized atomic utilization. However, single atoms often bond to the support with polarized electron density and thus exhibit a high valence state, limiting their catalytic scopes in many chemical transformations. In this study, it is demonstrated that 2D black phosphorus (BP) acts as giant phosphorus (P) ligand to confine a high density of single atoms (e.g., Pd1, Pt1) via atomic layer deposition. Unlike other 2D materials, BP with relatively low electronegativity and buckled structure favors the strong confinement of robust zero-valent palladium SACs in the vacancy site. Metallic Pd1/BP SAC shows a highly selective semi-hydrogenation of phenylacetylene toward styrene, distinct from metallic Pd nanoparticles that facilitate the formation of fully hydrogenated products. Density functional theory calculations reveal that Pd atom forms covalent-like bonding with adjacent P atoms, wherein H atoms tend to adsorb, aiding the dissociative adsorption of H2. Zero-valent Pd in the confined space favors a larger energy gain for the synthesis of partially hydrogenated product over the fully hydrogenated one. This work provides a new route toward the synthesis of zero-valent SACs on BP for organic transformations.

Authors:
 [1];  [2];  [3];  [4];  [5];  [6];  [3];  [3];  [7];  [7];  [3];  [3];  [8];  [9];  [3];  [3];  [3];  [6];  [4];  [10] more »;  [3];  [3] « less
+ Show Author Affiliations
  1. National Univ. of Singapore (Singapore); National Univ. of Singapore Research Institute, Suzhou (China)
  2. Shenzhen University (China)
  3. National Univ. of Singapore (Singapore)
  4. Agency for Science, Technology and Research (A*STAR) (Singapore)
  5. Nanyang Technological Univ. (Singapore)
  6. Univ. of Science and Technology of China, Hefei (China)
  7. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
  8. National Univ. of Singapore (Singapore); Northwestern Polytechnical Univ. (NPU), Xi'an (China)
  9. National Univ. of Singapore (Singapore); Shenzhen Univ. (China)
  10. Shenzhen Univ. (China)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Ministry of Education of Singapore (MOE); Nanyang Technological University; Shenzhen Peacock Plan; Shenzhen Innovation Program
OSTI Identifier:
1813966
Report Number(s):
BNL-221978-2021-JAAM
Journal ID: ISSN 0935-9648
Grant/Contract Number:  
SC0012704; MOE2017-T2-1-056; MOE2019-T2-2-044; R-143-000-A75-114; R-723-000-029-112; R-143-000-A63-114; 03INS000973C150; KQTD2016053112042971; JCYJ20190808142001745; RCJC20200714114434086
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Materials
Additional Journal Information:
Journal Volume: 33; Journal Issue: 35; Journal ID: ISSN 0935-9648
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; single-atom catalyst; zero valence; black phosphorus; reaction mechanisms

Citation Formats

Chen, Cheng, Ou, Wei, Yam, Kah‐Meng, Xi, Shibo, Zhao, Xiaoxu, Chen, Si, Li, Jing, Lyu, Pin, Ma, Lu, Du, Yonghua, Yu, Wei, Fang, Hanyan, Yao, Chuanhao, Hai, Xiao, Xu, Haomin, Koh, Ming Joo, Pennycook, Stephen J., Lu, Junling, Lin, Ming, Su, Chenliang, Zhang, Chun, and Lu, Jiong. Zero-Valent Palladium Single-Atoms Catalysts Confined in Black Phosphorus for Efficient Semi-Hydrogenation. United States: N. p., 2021. Web. doi:10.1002/adma.202008471.
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Chen, Cheng, Ou, Wei, Yam, Kah‐Meng, Xi, Shibo, Zhao, Xiaoxu, Chen, Si, Li, Jing, Lyu, Pin, Ma, Lu, Du, Yonghua, Yu, Wei, Fang, Hanyan, Yao, Chuanhao, Hai, Xiao, Xu, Haomin, Koh, Ming Joo, Pennycook, Stephen J., Lu, Junling, Lin, Ming, Su, Chenliang, Zhang, Chun, & Lu, Jiong. Zero-Valent Palladium Single-Atoms Catalysts Confined in Black Phosphorus for Efficient Semi-Hydrogenation. United States. https://doi.org/10.1002/adma.202008471
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Chen, Cheng, Ou, Wei, Yam, Kah‐Meng, Xi, Shibo, Zhao, Xiaoxu, Chen, Si, Li, Jing, Lyu, Pin, Ma, Lu, Du, Yonghua, Yu, Wei, Fang, Hanyan, Yao, Chuanhao, Hai, Xiao, Xu, Haomin, Koh, Ming Joo, Pennycook, Stephen J., Lu, Junling, Lin, Ming, Su, Chenliang, Zhang, Chun, and Lu, Jiong. Fri . "Zero-Valent Palladium Single-Atoms Catalysts Confined in Black Phosphorus for Efficient Semi-Hydrogenation". United States. https://doi.org/10.1002/adma.202008471. https://www.osti.gov/servlets/purl/1813966.
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@article{osti_1813966,
title = {Zero-Valent Palladium Single-Atoms Catalysts Confined in Black Phosphorus for Efficient Semi-Hydrogenation},
author = {Chen, Cheng and Ou, Wei and Yam, Kah‐Meng and Xi, Shibo and Zhao, Xiaoxu and Chen, Si and Li, Jing and Lyu, Pin and Ma, Lu and Du, Yonghua and Yu, Wei and Fang, Hanyan and Yao, Chuanhao and Hai, Xiao and Xu, Haomin and Koh, Ming Joo and Pennycook, Stephen J. and Lu, Junling and Lin, Ming and Su, Chenliang and Zhang, Chun and Lu, Jiong},
abstractNote = {Single-atom catalysts (SACs) represent a new frontier in heterogeneous catalysis due to their remarkable catalytic properties and maximized atomic utilization. However, single atoms often bond to the support with polarized electron density and thus exhibit a high valence state, limiting their catalytic scopes in many chemical transformations. In this study, it is demonstrated that 2D black phosphorus (BP) acts as giant phosphorus (P) ligand to confine a high density of single atoms (e.g., Pd1, Pt1) via atomic layer deposition. Unlike other 2D materials, BP with relatively low electronegativity and buckled structure favors the strong confinement of robust zero-valent palladium SACs in the vacancy site. Metallic Pd1/BP SAC shows a highly selective semi-hydrogenation of phenylacetylene toward styrene, distinct from metallic Pd nanoparticles that facilitate the formation of fully hydrogenated products. Density functional theory calculations reveal that Pd atom forms covalent-like bonding with adjacent P atoms, wherein H atoms tend to adsorb, aiding the dissociative adsorption of H2. Zero-valent Pd in the confined space favors a larger energy gain for the synthesis of partially hydrogenated product over the fully hydrogenated one. This work provides a new route toward the synthesis of zero-valent SACs on BP for organic transformations.},
doi = {10.1002/adma.202008471},
journal = {Advanced Materials},
number = 35,
volume = 33,
place = {United States},
year = {Fri Jul 23 00:00:00 EDT 2021},
month = {Fri Jul 23 00:00:00 EDT 2021}
}
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