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

Journal Article · · Proceedings of the National Academy of Sciences of the United States of America
 [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

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.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China (NSFC)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1460310
Journal Information:
Proceedings of the National Academy of Sciences of the United States of America, Vol. 115, Issue 17; ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 157 works
Citation information provided by
Web of Science

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Cited By (26)

Promise and Challenge of Phosphorus in Science, Technology, and Application journal September 2018
Black Phosphorus/Platinum Heterostructure: A Highly Efficient Photocatalyst for Solar-Driven Chemical Reactions journal September 2018
Recent Advances in Chemical Functionalization of 2D Black Phosphorous Nanosheets journal November 2019
Direct Z‐Scheme Hetero‐phase Junction of Black/Red Phosphorus for Photocatalytic Water Splitting journal July 2019
Chemistry of Layered Pnictogens: Phosphorus, Arsenic, Antimony, and Bismuth journal June 2019
Direct Z-Scheme Hetero-phase Junction of Black/Red Phosphorus for Photocatalytic Water Splitting journal July 2019
Black Phosphorus‐Based Semiconductor Heterojunctions for Photocatalytic Water Splitting journal January 2020
Band‐Gap and Charge Transfer Engineering in Red Phosphorus‐Based Composites for Enhanced Visible‐Light‐Driven H 2 Evolution journal January 2020
2D Elemental Nanomaterials Beyond Graphene journal June 2019
Construction of Defective Zinc–Cadmium–Sulfur Nanorods for Visible‐Light‐Driven Hydrogen Evolution Without the Use of Sacrificial Agents or Cocatalysts journal January 2020
Room Temperature Synthesis of Phosphine‐Capped Lead Bromide Perovskite Nanocrystals without Coordinating Solvents journal November 2019
Black Phosphorus, a Rising Star 2D Nanomaterial in the Post-Graphene Era: Synthesis, Properties, Modifications, and Photocatalysis Applications journal January 2019
Recent Progress on Black Phosphorus‐Based Materials for Photocatalytic Water Splitting journal September 2018
Efficient Production of Phosphorene Nanosheets via Shear Stress Mediated Exfoliation for Low‐Temperature Perovskite Solar Cells journal January 2019
Black phosphorus: an efficient co-catalyst for charge separation and enhanced photocatalytic hydrogen evolution journal August 2018
Black phosphorus nanoflakes/polyimide composite films with excellent dielectric and mechanical properties journal January 2020
Phosphorene: Current status, challenges and opportunities journal June 2019
Room-temperature pyro-catalytic hydrogen generation of 2D few-layer black phosphorene under cold-hot alternation journal July 2018
Solvent mediated hybrid 2D materials: black phosphorus – graphene heterostructured building blocks assembled for sodium ion batteries journal January 2018
p-Type BP nanosheet photocatalyst with AQE of 3.9% in the absence of a noble metal cocatalyst: investigation and elucidation of photophysical properties journal January 2018
Black/red phosphorus quantum dots for photocatalytic water splitting: from a type I heterostructure to a Z-scheme system journal January 2019
Partially-oxidized phosphorene sensor for the detection of sub-nano molar concentrations of nitric oxide: a first-principles study journal January 2019
An overview of the optical properties and applications of black phosphorus journal January 2020
Expressway to partially oxidized phosphorene journal April 2018
Chemistry of Layered Pnictogens: Phosphorus, Arsenic, Antimony, and Bismuth journal April 2019
A Low-Cost Metal-Free Photocatalyst Based on Black Phosphorus journal November 2018