Boron Doping and Defect Engineering of Graphene Aerogels for Ultrasensitive NO 2 Detection
Abstract
In this study, boron-doped and defect-engineered graphene aerogels are prepared using triphenyl boron as a boron precursor and subsequent heat treatments. The boron chemistry and concentration in the graphene lattice are found to be highly dependent on the temperature used to activate boron. At 1500 °C, boron is incorporated at 3.2 atom % through a combination of B–C, B–N, and B–O bonds. At 1750 °C, the boron concentration decreases to 0.7 atom % and is predominantly incorporated through B–N bonding. Higher temperatures result in complete expulsion of boron from the lattice, leaving behind defects that are found to be beneficial for NO2 gas detection. The gas sensing properties are explored to gain insight into the impact of boron chemistry on the sensing performance. A highly sensitive and selective conductometric NO2 sensor is fabricated on a low-power microheater. Defect-engineered graphene aerogels with no boron remaining have superior gas detection properties. At an optimum sensing temperature of 240 °C, the defect-engineered aerogel has a theoretical detection limit of 7 ppb for NO2 and response and recovery times of 100 and 300 s, respectively, with excellent selectivity over ammonia and hydrogen. Lastly, the superior gas sensing performance of defect-engineered graphene aerogels has remarkablemore »
- Authors:
-
- Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Univ. of California, Berkeley, CA (United States); Hangzhou Dianzi University (China)
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- Univ. of California, Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
- OSTI Identifier:
- 1548340
- Report Number(s):
- LLNL-JRNL-752424
Journal ID: ISSN 1932-7447; 938636
- Grant/Contract Number:
- AC52-07NA27344; AC02-05-CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 122; Journal Issue: 35; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Turner, Sally, Yan, Wenjun, Long, Hu, Nelson, Art J., Baker, Alex, Lee, Jonathan R. I., Carraro, Carlo, Worsley, Marcus A., Maboudian, Roya, and Zettl, Alex. Boron Doping and Defect Engineering of Graphene Aerogels for Ultrasensitive NO 2 Detection. United States: N. p., 2018.
Web. doi:10.1021/acs.jpcc.8b05984.
Turner, Sally, Yan, Wenjun, Long, Hu, Nelson, Art J., Baker, Alex, Lee, Jonathan R. I., Carraro, Carlo, Worsley, Marcus A., Maboudian, Roya, & Zettl, Alex. Boron Doping and Defect Engineering of Graphene Aerogels for Ultrasensitive NO 2 Detection. United States. https://doi.org/10.1021/acs.jpcc.8b05984
Turner, Sally, Yan, Wenjun, Long, Hu, Nelson, Art J., Baker, Alex, Lee, Jonathan R. I., Carraro, Carlo, Worsley, Marcus A., Maboudian, Roya, and Zettl, Alex. Tue .
"Boron Doping and Defect Engineering of Graphene Aerogels for Ultrasensitive NO 2 Detection". United States. https://doi.org/10.1021/acs.jpcc.8b05984. https://www.osti.gov/servlets/purl/1548340.
@article{osti_1548340,
title = {Boron Doping and Defect Engineering of Graphene Aerogels for Ultrasensitive NO 2 Detection},
author = {Turner, Sally and Yan, Wenjun and Long, Hu and Nelson, Art J. and Baker, Alex and Lee, Jonathan R. I. and Carraro, Carlo and Worsley, Marcus A. and Maboudian, Roya and Zettl, Alex},
abstractNote = {In this study, boron-doped and defect-engineered graphene aerogels are prepared using triphenyl boron as a boron precursor and subsequent heat treatments. The boron chemistry and concentration in the graphene lattice are found to be highly dependent on the temperature used to activate boron. At 1500 °C, boron is incorporated at 3.2 atom % through a combination of B–C, B–N, and B–O bonds. At 1750 °C, the boron concentration decreases to 0.7 atom % and is predominantly incorporated through B–N bonding. Higher temperatures result in complete expulsion of boron from the lattice, leaving behind defects that are found to be beneficial for NO2 gas detection. The gas sensing properties are explored to gain insight into the impact of boron chemistry on the sensing performance. A highly sensitive and selective conductometric NO2 sensor is fabricated on a low-power microheater. Defect-engineered graphene aerogels with no boron remaining have superior gas detection properties. At an optimum sensing temperature of 240 °C, the defect-engineered aerogel has a theoretical detection limit of 7 ppb for NO2 and response and recovery times of 100 and 300 s, respectively, with excellent selectivity over ammonia and hydrogen. Lastly, the superior gas sensing performance of defect-engineered graphene aerogels has remarkable implications for their performance in catalysis and energy storage applications.},
doi = {10.1021/acs.jpcc.8b05984},
journal = {Journal of Physical Chemistry. C},
number = 35,
volume = 122,
place = {United States},
year = {Tue Aug 14 00:00:00 EDT 2018},
month = {Tue Aug 14 00:00:00 EDT 2018}
}
Web of Science
Works referenced in this record:
Toward Macroscale, Isotropic Carbons with Graphene-Sheet-Like Electrical and Mechanical Properties
journal, April 2014
- Worsley, Marcus A.; Charnvanichborikarn, Supakit; Montalvo, Elizabeth
- Advanced Functional Materials, Vol. 24, Issue 27, p. 4259-4264
Synthesis of Graphene Aerogel with High Electrical Conductivity
journal, October 2010
- Worsley, Marcus A.; Pauzauskie, Peter J.; Olson, Tammy Y.
- Journal of the American Chemical Society, Vol. 132, Issue 40, p. 14067-14069
Synthesis and Characterization of Highly Crystalline Graphene Aerogels
journal, October 2014
- Worsley, Marcus A.; Pham, Thang T.; Yan, Aiming
- ACS Nano, Vol. 8, Issue 10, p. 11013-11022
Edge-to-Edge Assembled Graphene Oxide Aerogels with Outstanding Mechanical Performance and Superhigh Chemical Activity
journal, March 2013
- Huang, Huan; Chen, Pengwan; Zhang, Xuetong
- Small, Vol. 9, Issue 8
Mechanically strong and highly conductive graphene aerogel and its use as electrodes for electrochemical power sources
journal, January 2011
- Zhang, Xuetong; Sui, Zhuyin; Xu, Bin
- Journal of Materials Chemistry, Vol. 21, Issue 18
Catalytic hydrogen sensing using microheated platinum nanoparticle-loaded graphene aerogel
journal, January 2015
- Harley-Trochimczyk, Anna; Chang, Jiyoung; Zhou, Qin
- Sensors and Actuators B: Chemical, Vol. 206
Green synthesis of carbon nanotube–graphene hybrid aerogels and their use as versatile agents for water purification
journal, January 2012
- Sui, Zhuyin; Meng, Qinghan; Zhang, Xuetong
- Journal of Materials Chemistry, Vol. 22, Issue 18
Deposition of Three-Dimensional Graphene Aerogel on Nickel Foam as a Binder-Free Supercapacitor Electrode
journal, July 2013
- Ye, Shibing; Feng, Jiachun; Wu, Peiyi
- ACS Applied Materials & Interfaces, Vol. 5, Issue 15
Toward New Candidates for Hydrogen Storage: High-Surface-Area Carbon Aerogels
journal, December 2006
- Kabbour, Houria; Baumann, Theodore F.; Satcher,, Joe H.
- Chemistry of Materials, Vol. 18, Issue 26, p. 6085-6087
Hierarchically Porous Graphene as a Lithium–Air Battery Electrode
journal, November 2011
- Xiao, Jie; Mei, Donghai; Li, Xiaolin
- Nano Letters, Vol. 11, Issue 11
Carbon-Based Supercapacitors Produced by Activation of Graphene
journal, May 2011
- Zhu, Y.; Murali, S.; Stoller, M. D.
- Science, Vol. 332, Issue 6037, p. 1537-1541
Can Boron and Nitrogen Co-doping Improve Oxygen Reduction Reaction Activity of Carbon Nanotubes?
journal, January 2013
- Zhao, Yu; Yang, Lijun; Chen, Sheng
- Journal of the American Chemical Society, Vol. 135, Issue 4
Boron- and Nitrogen-Substituted Graphene Nanoribbons as Efficient Catalysts for Oxygen Reduction Reaction
journal, February 2015
- Gong, Yongji; Fei, Huilong; Zou, Xiaolong
- Chemistry of Materials, Vol. 27, Issue 4
First-Principles Study of Nitrogen-, Boron-Doped Graphene and Co-Doped Graphene as the Potential Catalysts in Nonaqueous Li–O 2 Batteries
journal, March 2016
- Jiang, H. R.; Zhao, T. S.; Shi, L.
- The Journal of Physical Chemistry C, Vol. 120, Issue 12
Synthesis, Structure, and Properties of Boron- and Nitrogen-Doped Graphene
journal, August 2009
- Panchakarla, L. S.; Subrahmanyam, K. S.; Saha, S. K.
- Advanced Materials
Nitrogen-Doped Graphene as Efficient Metal-Free Electrocatalyst for Oxygen Reduction in Fuel Cells
journal, February 2010
- Qu, Liangti; Liu, Yong; Baek, Jong-Beom
- ACS Nano, Vol. 4, Issue 3, p. 1321-1326
Adsorption of hydrogen on boron-doped graphene: A first-principles prediction
journal, January 2009
- Zhou, Y. G.; Zu, X. T.; Gao, F.
- Journal of Applied Physics, Vol. 105, Issue 1
Improving gas sensing properties of graphene by introducing dopants and defects: a first-principles study
journal, April 2009
- Zhang, Yong-Hui; Chen, Ya-Bin; Zhou, Kai-Ge
- Nanotechnology, Vol. 20, Issue 18
Ultrasensitive gas detection of large-area boron-doped graphene
journal, November 2015
- Lv, Ruitao; Chen, Gugang; Li, Qing
- Proceedings of the National Academy of Sciences, Vol. 112, Issue 47
Sandwiched Fe 3 O 4 /Carboxylate Graphene Oxide Nanostructures Constructed by Layer-by-Layer Assembly for Highly Efficient and Magnetically Recyclable Dye Removal
journal, November 2017
- Guo, Rong; Jiao, Tifeng; Li, Ruifei
- ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 1
Self-Assembled AgNP-Containing Nanocomposites Constructed by Electrospinning as Efficient Dye Photocatalyst Materials for Wastewater Treatment
journal, January 2018
- Liu, Yamei; Hou, Caili; Jiao, Tifeng
- Nanomaterials, Vol. 8, Issue 1
Graphene Oxide-Polymer Composite Langmuir Films Constructed by Interfacial Thiol-Ene Photopolymerization
journal, February 2017
- Luo, Xiaona; Ma, Kai; Jiao, Tifeng
- Nanoscale Research Letters, Vol. 12, Issue 1
Self-Assembled Graphene Hydrogel via a One-Step Hydrothermal Process
journal, July 2010
- Xu, Yuxi; Sheng, Kaixuan; Li, Chun
- ACS Nano, Vol. 4, Issue 7, p. 4324-4330
Porous B-doped graphene inspired by Fried-Ice for supercapacitors and metal-free catalysts
journal, January 2013
- Zuo, Zicheng; Jiang, Zhongqing; Manthiram, Arumugam
- Journal of Materials Chemistry A, Vol. 1, Issue 43
Electrochemical doping of three-dimensional graphene networks used as efficient electrocatalysts for oxygen reduction reaction
journal, January 2015
- Wang, Zhijuan; Cao, Xiehong; Ping, Jianfeng
- Nanoscale, Vol. 7, Issue 21
Two-step synthesis of boron and nitrogen co-doped graphene as a synergistically enhanced catalyst for the oxygen reduction reaction
journal, January 2014
- Tai, Jiapo; Hu, Jiantong; Chen, Zhongxin
- RSC Adv., Vol. 4, Issue 106
Catalyst-Free Synthesis of Crumpled Boron and Nitrogen Co-Doped Graphite Layers with Tunable Bond Structure for Oxygen Reduction Reaction
journal, March 2014
- Jin, Jutao; Pan, Fuping; Jiang, Luhua
- ACS Nano, Vol. 8, Issue 4
Effect of Boron-Doping on the Graphene Aerogel Used as Cathode for the Lithium–Sulfur Battery
journal, November 2015
- Xie, Yang; Meng, Zhen; Cai, Tingwei
- ACS Applied Materials & Interfaces, Vol. 7, Issue 45
Detection of individual gas molecules adsorbed on graphene
journal, July 2007
- Schedin, F.; Geim, A. K.; Morozov, S. V.
- Nature Materials, Vol. 6, Issue 9, p. 652-655
3D Fe 3 O 4 nanoparticle/graphene aerogel for NO 2 sensing at room temperature
journal, January 2015
- Liu, Xin; Li, Jinwei; Sun, Jianbo
- RSC Advances, Vol. 5, Issue 90
High Surface Area MoS 2 /Graphene Hybrid Aerogel for Ultrasensitive NO 2 Detection
journal, May 2016
- Long, Hu; Harley-Trochimczyk, Anna; Pham, Thang
- Advanced Functional Materials, Vol. 26, Issue 28
Enhanced electrochemical performance of ion-beam-treated 3D graphene aerogels for lithium ion batteries
journal, April 2015
- Ye, J. C.; Charnvanichborikarn, S.; Worsley, M. A.
- Carbon, Vol. 85
Raman Spectroscopy of Boron-Doped Single-Layer Graphene
journal, June 2012
- Kim, Yoong Ahm; Fujisawa, Kazunori; Muramatsu, Hiroyuki
- ACS Nano, Vol. 6, Issue 7
Phase stability of boron carbon nitride in a heterographene structure: A first-principles study
journal, April 2009
- Yuge, Koretaka
- Physical Review B, Vol. 79, Issue 14
Self healing of defected graphene
journal, March 2013
- Chen, Jianhui; Shi, Tuwan; Cai, Tuocheng
- Applied Physics Letters, Vol. 102, Issue 10
Graphene healing mechanisms: A theoretical investigation
journal, April 2016
- Botari, Tiago; Paupitz, Ricardo; Alves da Silva Autreto, Pedro
- Carbon, Vol. 99
The Near Edge Structure of Hexagonal Boron Nitride
journal, April 2014
- McDougall, Nicholas L.; Nicholls, Rebecca J.; Partridge, Jim G.
- Microscopy and Microanalysis, Vol. 20, Issue 4
Local structure analysis of boron-doped graphite by soft x-ray emission and absorption spectroscopy using synchrotron radiation
journal, September 2011
- Hanafusa, Atsushi; Muramatsu, Yasuji; Kaburagi, Yutaka
- Journal of Applied Physics, Vol. 110, Issue 5
Molecular Doping of Graphene
journal, January 2008
- Wehling, T. O.; Novoselov, K. S.; Morozov, S. V.
- Nano Letters, Vol. 8, Issue 1
All-Organic Vapor Sensor Using Inkjet-Printed Reduced Graphene Oxide
journal, March 2010
- Dua, Vineet; Surwade, Sumedh P.; Ammu, Srikanth
- Angewandte Chemie International Edition, Vol. 49, Issue 12
Defect engineering of graphene for effective hydrogen storage
journal, March 2014
- Yadav, Shwetank; Zhu, Zhihui; Singh, Chandra Veer
- International Journal of Hydrogen Energy, Vol. 39, Issue 10
Works referencing / citing this record:
Recent Advances of Porous Graphene: Synthesis, Functionalization, and Electrochemical Applications
journal, October 2019
- Zhang, Yuanyuan; Wan, Qijin; Yang, Nianjun
- Small, Vol. 15, Issue 48
On-chip assembly of 3D graphene-based aerogels for chemiresistive gas sensing
journal, January 2020
- Shao, Gaofeng; Ovsianytskyi, Oleksandr; Bekheet, Maged F.
- Chemical Communications, Vol. 56, Issue 3
Boron-doped few-layer graphene nanosheet gas sensor for enhanced ammonia sensing at room temperature
journal, January 2020
- Srivastava, Shubhda; Jain, Shubhendra K.; Gupta, Govind
- RSC Advances, Vol. 10, Issue 2