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Title: Facile bottom-up synthesis of partially oxidized black phosphorus nanosheets as metal-free photocatalyst for hydrogen evolution

Abstract

Few-layer black phosphorus (BP) nanosheets were first reported as a 2D material for the application of field-effect transistors in 2014 and have stimulated intense activity among physicists, chemists, and material and biomedical scientists, driving research into novel synthetic techniques to produce BP nanosheets. At present, exfoliation is the main route toward few-layer BP nanosheets via employing bulk BP as raw material. However, this is a complicated and time-consuming process, which is difficult for the large-scale synthesis of BP nanosheets. Moreover, BP degrades rapidly when exfoliated to nanoscale dimensions, resulting in the rapid loss of semiconducting properties. Here in this paper, we report the direct wet-chemical synthesis of few-layer BP nanosheets in gram-scale quantities in a bottom-up approach based on common laboratory reagents at low temperature, showing excellent stability due to partial oxidation of surface. Solvent and temperature are two critical factors, controlling not only the formation of BP nanosheets but also the thickness. The as-prepared BP nanosheets can extract hydrogen from pure water (pH = 6.8), exhibiting more than 24-fold higher activity than the well-known C 3N 4 nanosheets. Our results reporting the ability to prepare few-layer BP nanosheets with a facile, scalable, low-cost approach take us a step closermore » to real-world applications of phosphorene including next-generation metal-free photocatalysts for photosynthesis.« less

Authors:
 [1];  [1];  [2];  [2];  [1];  [3]; ORCiD logo [4];  [5]
  1. Taiyuan Univ. of Technology, Taiyuan (China). Key Lab. of Advanced Transducers and Intelligent Control System of Ministry of Education, College of Physics and Optoelectronics
  2. Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
  3. Dalian Nationalities Univ., Liaoning, Dalian (China). College of Life Science
  4. Taiyuan Univ. of Technology, Taiyuan (China). Key Lab. of Advanced Transducers and Intelligent Control System of Ministry of Education, College of Physics and Optoelectronics; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Natural Science Foundation of China (NNSFC)
OSTI Identifier:
1460310
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 115; Journal Issue: 17; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 08 HYDROGEN; hydrogen evolution; photocatalysis; bottom-up synthesis; 2D materials; black phosphorus; BP

Citation Formats

Tian, Bin, Tian, Bining, Smith, Bethany, Scott, M. C., Lei, Qin, Hua, Ruinian, Tian, Yue, and Liu, Yi. Facile bottom-up synthesis of partially oxidized black phosphorus nanosheets as metal-free photocatalyst for hydrogen evolution. United States: N. p., 2018. Web. doi:10.1073/pnas.1800069115.
Tian, Bin, Tian, Bining, Smith, Bethany, Scott, M. C., Lei, Qin, Hua, Ruinian, Tian, Yue, & Liu, Yi. Facile bottom-up synthesis of partially oxidized black phosphorus nanosheets as metal-free photocatalyst for hydrogen evolution. United States. doi:10.1073/pnas.1800069115.
Tian, Bin, Tian, Bining, Smith, Bethany, Scott, M. C., Lei, Qin, Hua, Ruinian, Tian, Yue, and Liu, Yi. Wed . "Facile bottom-up synthesis of partially oxidized black phosphorus nanosheets as metal-free photocatalyst for hydrogen evolution". United States. doi:10.1073/pnas.1800069115. https://www.osti.gov/servlets/purl/1460310.
@article{osti_1460310,
title = {Facile bottom-up synthesis of partially oxidized black phosphorus nanosheets as metal-free photocatalyst for hydrogen evolution},
author = {Tian, Bin and Tian, Bining and Smith, Bethany and Scott, M. C. and Lei, Qin and Hua, Ruinian and Tian, Yue and Liu, Yi},
abstractNote = {Few-layer black phosphorus (BP) nanosheets were first reported as a 2D material for the application of field-effect transistors in 2014 and have stimulated intense activity among physicists, chemists, and material and biomedical scientists, driving research into novel synthetic techniques to produce BP nanosheets. At present, exfoliation is the main route toward few-layer BP nanosheets via employing bulk BP as raw material. However, this is a complicated and time-consuming process, which is difficult for the large-scale synthesis of BP nanosheets. Moreover, BP degrades rapidly when exfoliated to nanoscale dimensions, resulting in the rapid loss of semiconducting properties. Here in this paper, we report the direct wet-chemical synthesis of few-layer BP nanosheets in gram-scale quantities in a bottom-up approach based on common laboratory reagents at low temperature, showing excellent stability due to partial oxidation of surface. Solvent and temperature are two critical factors, controlling not only the formation of BP nanosheets but also the thickness. The as-prepared BP nanosheets can extract hydrogen from pure water (pH = 6.8), exhibiting more than 24-fold higher activity than the well-known C3N4 nanosheets. Our results reporting the ability to prepare few-layer BP nanosheets with a facile, scalable, low-cost approach take us a step closer to real-world applications of phosphorene including next-generation metal-free photocatalysts for photosynthesis.},
doi = {10.1073/pnas.1800069115},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 17,
volume = 115,
place = {United States},
year = {2018},
month = {3}
}

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