Modifying Carbon Nitride through Extreme Phosphorus Substitution
Abstract
In this work, a glassy carbon phosphonitride material with bulk chemical composition roughly approximating C3N3P was synthesized through a high-pressure, high-temperature process using a pure P(CN)3 molecular precursor. The resulting material (hereafter referred to as “HPHT-C3N3P”) was characterized using a variety of techniques, including X-ray scattering, pair distribution function analysis, 31P, 13C, 15N magic-angle spinning nuclear magnetic resonance spectroscopies; X-ray photoelectron spectroscopy, and Raman and IR spectroscopies. The measurements indicate that HPHT-C3N3P lacks long-range structural order with a local structure predominantly composed of a sp2, s-triazine-like network in which phosphorus atoms substitute for bridging nitrogen sites found in related C3N4 materials. The HPHT-C3N3P sample exhibits semiconducting properties, with electrical transport dominated by variable-range hopping. The high phosphorus content of HPHT-C3N3P (approaching 13 at. %) is associated with a major decrease in the optical absorption edge (~0.4 eV) and a ~1010-fold increase in electrical conductivity, as compared to previously-reported P-doped graphitic g-C3N4 (0.6-3.8 at. % P). The HPHT-C3N3P sample is considerably harder than layered g-C3N4 and exhibits superior thermal stability up to ~700 °C in air. These results demonstrate a remarkable range of tunable properties possible for C3N4-related materials through elemental substitution and provide valuable information to guide the design ofmore »
- Authors:
-
[3];
[4];
[4];
[1]
- Carnegie Inst. for Science, Washington, DC (United States)
- Carnegie Inst. for Science, Washington, DC (United States); Center for High Pressure Science and Technology Advanced Research, Beijing (China)
- Pennsylvania State Univ., University Park, PA (United States)
- Naval Research Lab., Washington, DC (United States)
- The George Washington Univ., Washington, DC (United States)
- Yanshan Univ., Qinhuangdao (China)
- Universität zu Köln (Germany)
- Univ. of Chicago, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Sponsoring Org.:
- Defense Advanced Research Projects Agency (DARPA); US Army Research Office (ARO); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
- OSTI Identifier:
- 1526061
- Grant/Contract Number:
- W31P4Q-13-1-0005; FG02-94ER14466; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Materials Letters
- Additional Journal Information:
- Journal Volume: 1; Journal Issue: 1; Journal ID: ISSN 2639-4979
- Publisher:
- ACS Publications
- Country of Publication:
- United States
- Language:
- ENGLISH
- Subject:
- 36 MATERIALS SCIENCE; Inorganic carbon compounds; Electrical conductivity; Phosphorus; Carbon; Materials
Citation Formats
Wang, Qianqian, Gou, Huiyang, Zhu, Li, Huang, Haw-Tyng, Biswas, Arani, Chaloux, Brian L., Epshteyn, Albert, Yesinowski, James P., Liu, Zhenxian, Cody, George, Ma, Mengdong, Zhao, Zhisheng, Fei, Yingwei, Prescher, Clemens, Greenberg, Eran, Prakapenka, Vitali B., and Strobel, Timothy A. Modifying Carbon Nitride through Extreme Phosphorus Substitution. United States: N. p., 2019.
Web. doi:10.1021/acsmaterialslett.9b00010.
Wang, Qianqian, Gou, Huiyang, Zhu, Li, Huang, Haw-Tyng, Biswas, Arani, Chaloux, Brian L., Epshteyn, Albert, Yesinowski, James P., Liu, Zhenxian, Cody, George, Ma, Mengdong, Zhao, Zhisheng, Fei, Yingwei, Prescher, Clemens, Greenberg, Eran, Prakapenka, Vitali B., & Strobel, Timothy A. Modifying Carbon Nitride through Extreme Phosphorus Substitution. United States. https://doi.org/10.1021/acsmaterialslett.9b00010
Wang, Qianqian, Gou, Huiyang, Zhu, Li, Huang, Haw-Tyng, Biswas, Arani, Chaloux, Brian L., Epshteyn, Albert, Yesinowski, James P., Liu, Zhenxian, Cody, George, Ma, Mengdong, Zhao, Zhisheng, Fei, Yingwei, Prescher, Clemens, Greenberg, Eran, Prakapenka, Vitali B., and Strobel, Timothy A. Tue .
"Modifying Carbon Nitride through Extreme Phosphorus Substitution". United States. https://doi.org/10.1021/acsmaterialslett.9b00010. https://www.osti.gov/servlets/purl/1526061.
@article{osti_1526061,
title = {Modifying Carbon Nitride through Extreme Phosphorus Substitution},
author = {Wang, Qianqian and Gou, Huiyang and Zhu, Li and Huang, Haw-Tyng and Biswas, Arani and Chaloux, Brian L. and Epshteyn, Albert and Yesinowski, James P. and Liu, Zhenxian and Cody, George and Ma, Mengdong and Zhao, Zhisheng and Fei, Yingwei and Prescher, Clemens and Greenberg, Eran and Prakapenka, Vitali B. and Strobel, Timothy A.},
abstractNote = {In this work, a glassy carbon phosphonitride material with bulk chemical composition roughly approximating C3N3P was synthesized through a high-pressure, high-temperature process using a pure P(CN)3 molecular precursor. The resulting material (hereafter referred to as “HPHT-C3N3P”) was characterized using a variety of techniques, including X-ray scattering, pair distribution function analysis, 31P, 13C, 15N magic-angle spinning nuclear magnetic resonance spectroscopies; X-ray photoelectron spectroscopy, and Raman and IR spectroscopies. The measurements indicate that HPHT-C3N3P lacks long-range structural order with a local structure predominantly composed of a sp2, s-triazine-like network in which phosphorus atoms substitute for bridging nitrogen sites found in related C3N4 materials. The HPHT-C3N3P sample exhibits semiconducting properties, with electrical transport dominated by variable-range hopping. The high phosphorus content of HPHT-C3N3P (approaching 13 at. %) is associated with a major decrease in the optical absorption edge (~0.4 eV) and a ~1010-fold increase in electrical conductivity, as compared to previously-reported P-doped graphitic g-C3N4 (0.6-3.8 at. % P). The HPHT-C3N3P sample is considerably harder than layered g-C3N4 and exhibits superior thermal stability up to ~700 °C in air. These results demonstrate a remarkable range of tunable properties possible for C3N4-related materials through elemental substitution and provide valuable information to guide the design of new materials.},
doi = {10.1021/acsmaterialslett.9b00010},
journal = {ACS Materials Letters},
number = 1,
volume = 1,
place = {United States},
year = {Tue Mar 26 00:00:00 EDT 2019},
month = {Tue Mar 26 00:00:00 EDT 2019}
}
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