Nitrogen‐Doped Carbon Nanotube Arrays for High‐Efficiency Electrochemical Reduction of CO 2 : On the Understanding of Defects, Defect Density, and Selectivity
Abstract
Nitrogen‐doped carbon nanotubes (NCNTs) have been considered as a promising electrocatalyst for carbon‐dioxide‐reduction reactions, but two fundamental chemistry questions remain obscure: 1) What are the active centers with respect to various defect species and 2) what is the role of defect density on the selectivity of NCNTs? The aim of this work is to address these questions. The catalytic activity of NCNTs depends on the structural nature of nitrogen in CNTs and defect density. Comparing with pristine CNTs, the presence of graphitic and pyridinic nitrogen significantly decreases the overpotential (ca. −0.18 V) and increases the selectivity (ca. 80 %) towards the formation of CO. The experimental results are in congruent with DFT calculations, which show that pyridinic defects retain a lone pair of electrons that are capable of binding CO 2 . However, for graphitic‐like nitrogen, electrons are located in the π* antibonding orbital, making them less accessible for CO 2 binding.
Integrity signals
Registry
Cites
Statistics
Claims the paper makes
Claims other papers make about this one
Each is checked against this paper’s own text: does it say what the citing paper says it does?
Various studies have utilized bulk sensitive in situ XANES spectroscopy to show that Cu+ is stable during the course of CO2RR, a finding recently supported by another study using in situ soft XAS measurements.
“Various studies [100,101] have utilized bulk sensitive in situ X-ray absorption near-edge structure (XANES) spectroscopy to show that Cu + is stable during the course of CO2RR, a finding recently supported by another study using in situ soft XAS measurements (Figure .6a,b).[102]”
From Electrochemical CO <sub>2</sub> Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design (2019) · cites this paper as [102]
Cites
Nitrogen-Doped Carbon Nanotube Arrays with High Electrocatalytic Activity for Oxygen Reduction
Gong, K., Du, F., Xia, Z., Durstock, M. F., & Dai, L. (2009) · Science · doi:10.1126/science.1168049 · Cited by 7,183 · see citing works
Lai, L., Potts, J. R., Zhan, D., Wang, L., Poh, C. K., Tang, C., Gong, H., Shen, Z., Lin, J., & Ruoff, R. S. (2012) · Energy & Environmental Science · doi:10.1039/c2ee21802j · Cited by 2,275 · see citing works
Hori, Y., Wakebe, H., Tsukamoto, T., & Koga, O. (1994) · Electrochimica Acta · doi:10.1016/0013-4686(94)85172-7 · Cited by 2,140 · see citing works
An oxygen reduction electrocatalyst based on carbon nanotube–graphene complexes
Li, Y., Zhou, W., Wang, H., Xie, L., Liang, Y., Wei, F., Idrobo, J. C., Pennycook, S. J., & Dai, H. (2012) · Nature Nanotechnology · doi:10.1038/nnano.2012.72 · Cited by 1,620 · see citing works
Ionic Liquid–Mediated Selective Conversion of CO <sub>2</sub> to CO at Low Overpotentials
Rosen, B. A., Salehi-Khojin, A., Thorson, M. R., Zhu, W., Whipple, D. T., Kenis, P. J. A., & Masel, R. I. (2011) · Science · doi:10.1126/science.1209786 · Cited by 1,558 · see citing works
Prospects of CO 2 Utilization via Direct Heterogeneous Electrochemical Reduction
Whipple, D. T., & Kenis, P. J. A. (2010) · The Journal of Physical Chemistry Letters · doi:10.1021/jz1012627 · Cited by 1,419 · see citing works
Catalysis Research of Relevance to Carbon Management: Progress, Challenges, and Opportunities
Arakawa, H., Aresta, M., Armor, J. N., Barteau, M. A., Beckman, E. J., Bell, A. T., Bercaw, J. E., Creutz, C., Dinjus, E., Dixon, D. A., et al. (2001) · Chemical Reviews · doi:10.1021/cr000018s · Cited by 1,410 · see citing works
Anthropogenic Chemical Carbon Cycle for a Sustainable Future
Olah, G. A., Prakash, G. K. S., & Goeppert, A. (2011) · Journal of the American Chemical Society · doi:10.1021/ja202642y · Cited by 1,378 · see citing works
Liu, R.-L., Wu, D.-Q., Feng, X.-L., & Müllen, K. (2010) · Angewandte Chemie · doi:10.1002/anie.200907289 · Cited by 1,358 · see citing works
Toward N-Doped Graphene via Solvothermal Synthesis
Deng, D., Pan, X., Yu, L., Cui, Y., Jiang, Y., Qi, J., Li, W., Fu, Q., Ma, X.-C., Xue, Q., et al. (2011) · Chemistry of Materials · doi:10.1021/cm102666r · Cited by 1,066 · see citing works
Nanoporous Graphitic-C3N4@Carbon Metal-Free Electrocatalysts for Highly Efficient Oxygen Reduction
Zheng, Y., Jiao, Y., Chen, J., Liu, J., Liang, J., Du, A., Zhang, W., Zhu, Z., Smith, S. C., Jaroniec, M., et al. (2011) · Journal of the American Chemical Society · doi:10.1021/ja209206c · Cited by 1,037 · see citing works
Persistent growth of CO2 emissions and implications for reaching climate targets
Friedlingstein, P., Andrew, R. M., Rogelj, J., Peters, G. P., Canadell, J. G., Knutti, R., Luderer, G., Raupach, M. R., Schaeffer, M., van Vuuren, D. P., et al. (2014) · Nature Geoscience · doi:10.1038/ngeo2248 · Cited by 771 · see citing works
Wang, S., Yu, D., & Dai, L. (2011) · Journal of the American Chemical Society · doi:10.1021/ja1112904 · Cited by 724 · see citing works
Renewable and metal-free carbon nanofibre catalysts for carbon dioxide reduction
Kumar, B., Asadi, M., Pisasale, D., Sinha‐Ray, S., Rosen, B. A., Haasch, R. T., Abiade, J. T., Yarin, A. L., & Salehi‐Khojin, A. (2013) · Nature Communications · doi:10.1038/ncomms3819 · Cited by 698 · see citing works
Zhang, S., Kang, P., Ubnoske, S. M., Brennaman, M. K., Song, N., House, R. L., Glass, J. T., & Meyer, T. J. (2014) · Journal of the American Chemical Society · doi:10.1021/ja5031529 · Cited by 659 · see citing works
Rao, C. V., Cabrera, C. R., & Ishikawa, Y. (2010) · The Journal of Physical Chemistry Letters · doi:10.1021/jz100971v · Cited by 636 · see citing works
Kundu, S., Nagaiah, T. C., Xia, W., Wang, Y., van Dommele, S., Bitter, J. H., Santa, M., Grundmeier, G., Bron, M., Schuhmann, W. W., et al. (2009) · The Journal of Physical Chemistry C · doi:10.1021/jp811320d · Cited by 559 · see citing works
Liu, R., Wu, D., Feng, X., & Müllen, K. (2010) · Angewandte Chemie · doi:10.1002/ange.200907289 · Cited by 464 · see citing works
Chen, Z., Higgins, D. C., Tao, H., Hsu, R. S., & Chen, Z. (2009) · The Journal of Physical Chemistry C · doi:10.1021/jp908067v · Cited by 370 · see citing works
Structural and morphological control of aligned nitrogen-doped carbon nanotubes
Liu, H., Zhang, Y. A., Li, R., Sun, X. A., Désilets, S., Abou‐Rachid, H., Jaidann, M., & Lussier, L. S. (2009) · Carbon · doi:10.1016/j.carbon.2009.12.045 · Cited by 369 · see citing works
Noda, H., Ikeda, S., Oda, Y., IMAI, K., Maeda, M., & Ito, K. (1990) · Bulletin of the Chemical Society of Japan · doi:10.1246/bcsj.63.2459 · Cited by 257 · see citing works
Influence of diameter in the Raman spectra of aligned multi-walled carbon nanotubes
Antunes, E. F., Lobo, A. O., Corat, E. J., & Trava-Airoldi, V. J. (2007) · Carbon · doi:10.1016/j.carbon.2007.01.003 · Cited by 243 · see citing works
Effect of electrochemical polarization of PtRu/C catalysts on methanol electrooxidation
Wu, G., Li, L., & Xu, B. (2004) · Electrochimica Acta · doi:10.1016/j.electacta.2004.07.006 · Cited by 239 · see citing works
Oxygen molecule dissociation on carbon nanostructures with different types of nitrogen doping
Ni, S., Li, Z., & Yang, J. (2011) · Nanoscale · doi:10.1039/c1nr11086a · Cited by 235 · see citing works
Wu, J., Risalvato, F. G., Ke, F., Pellechia, P. J., & Zhou, X. (2012) · Journal of The Electrochemical Society · doi:10.1149/2.049207jes · Cited by 216 · see citing works
Self-citationEthanol electro-oxidation on Pt/C and PtSn/C catalysts in alkaline and acid solutions
Jiang, L., Hsu, A., Chu, D., & Chen, R. (2009) · International Journal of Hydrogen Energy · doi:10.1016/j.ijhydene.2009.10.058 · Cited by 204 · see citing works
Mo, Z., Liao, S., Zheng, Y., & Fu, Z. (2012) · Carbon · doi:10.1016/j.carbon.2012.02.021 · Cited by 179 · see citing works
Wu, J., Risalvato, F. G., Ma, S., & Zhou, X. (2013) · Journal of Materials Chemistry A · doi:10.1039/c3ta13544f · Cited by 168 · see citing works
Self-citationOxygen reduction on copper in neutral NaCl solution
King, F., Quinn, M. J., & Litke, C. D. (1995) · Journal of Electroanalytical Chemistry · doi:10.1016/0022-0728(94)03705-8 · Cited by 142 · see citing works
Ma, G., Jia, R., Zhao, J., et al. (2011) · The Journal of Physical Chemistry C · doi:10.1021/jp208257r · Cited by 134 · see citing works
Koós, A. A., Dowling, M., Jurkschat, K., et al. (2008) · Carbon · doi:10.1016/j.carbon.2008.08.014 · Cited by 132 · see citing works
Yadav, R. M., Wu, J., Raji, K., Ma, L., Tiwary, C. S., Ge, L., Ye, G., Vajtai, R., Lou, J., & Ajayan, P. M. (2015) · ACS Applied Materials & Interfaces · doi:10.1021/acsami.5b02032 · Cited by 124 · see citing works
Self-citationElectrochemical Reduction of Carbon Dioxide
Wu, J., Risalvato, F. G., Sharma, P. P., Pellechia, P. J., Ke, F., & Zhou, X. (2013) · Journal of The Electrochemical Society · doi:10.1149/2.030309jes · Cited by 106 · see citing works
Self-citationBaranton, S., Coutanceau, C., Garnier, E., & Léger, J. (2006) · Journal of Electroanalytical Chemistry · doi:10.1016/j.jelechem.2006.03.007 · Cited by 96 · see citing works
Sumpter, B. G., Huang, J., Meunier, V. C., et al. (2008) · International Journal of Quantum Chemistry · doi:10.1002/qua.21893 · Cited by 75 · see citing works
Zhong, S., Zhou, L., Wu, L., Lianfeng, T., He, Q., & Ahmed, J. (2014) · Journal of Power Sources · doi:10.1016/j.jpowsour.2014.08.114 · Cited by 72 · see citing works
Kinetics of oxygen reduction at RuO2-coated titanium electrode in alkaline solution
Chang, C. C., & Wen, T. (1997) · Journal of Applied Electrochemistry · doi:10.1023/a:1018445100515 · Cited by 41 · see citing works
Flagged first, then by citations
Cited by
Sorted by citations
Kibria, M. G., Edwards, J. P., Gabardo, C. M., Dinh, C., Seifitokaldani, A., Sinton, D., & Sargent, E. H. (2019) · Advanced Materials · doi:10.1002/adma.201807166 · Cited by 1,331 · see citing works
Electrocatalysis for CO <sub>2</sub> conversion: from fundamentals to value-added products
Wang, G., Chen, J., Ding, Y., Cai, P., Yi, L., Li, Y., Tu, C., Hou, Y., Wen, Z., & Dai, L. (2021) · Chemical Society Reviews · doi:10.1039/d0cs00071j · Cited by 1,295 · see citing works
Large-Scale and Highly Selective CO2 Electrocatalytic Reduction on Nickel Single-Atom Catalyst
Zheng, T., Jiang, K., Ta, N., Hu, Y., Zeng, J., Liu, J., & Wang, H. (2019) · Joule · doi:10.1016/j.joule.2018.10.015 · Cited by 887 · see citing works
Metal‐Free Carbon Materials for CO<sub>2</sub> Electrochemical Reduction
Duan, X., Xu, J., Wei, Z., Ma, J., Guo, S., Wang, S., Liu, H., & Dou, S. (2017) · Advanced Materials · doi:10.1002/adma.201701784 · Cited by 754 · see citing works
Wu, J., Liu, M., Sharma, P. P., Yadav, R. M., Ma, L., Yang, Y., Zou, X., Zhou, X.-D., Vajtai, R., Yakobson, B. I., et al. (2016) · Nano Letters · doi:10.1021/acs.nanolett.5b04123 · Cited by 520 · see citing works
Self-citationJiang, K., Siahrostami, S., Akey, A. J., Li, Y., Lu, Z., Lattimer, J., Hu, Y., Stokes, C., Gangishetty, M., Chen, G., et al. (2017) · Chem · doi:10.1016/j.chempr.2017.09.014 · Cited by 406 · see citing works
Larrazábal, G. O., Martín, A. J., & Pérez-Ramírez, J. (2017) · The Journal of Physical Chemistry Letters · doi:10.1021/acs.jpclett.7b01380 · Cited by 176 · see citing works
Chen, W. Q., Fu, X., Veksha, A., Lipik, V., & Lisak, G. (2022) · Journal of Cleaner Production · doi:10.1016/j.jclepro.2022.131868 · Cited by 37 · see citing works
Sharma, P. P., & Zhou, X. (2017) · WIREs Energy and Environment · doi:10.1002/wene.239 · Cited by 28 · see citing works
Self-citation
- Authors
- Sharma, P. P., Wu, J., Yadav, R. M., Liu, M., Wright, C. J., Tiwary, C. S., Yakobson, B. I., Lou, J., Ajayan, P. M., & Zhou, X.
- Affiliations
- University of South Carolina (US)
- Rice University (US)
- Corresponding author
- Lou, Jun
- Ajayan, Pulickel M.
- Zhou, Xiao‐Dong
- ORCID
- Venue
- Angewandte Chemie International Edition
- Publisher
- Wiley
- Published
- 2015-09-25
- Volume
- 54
- Issue
- 46
- Pages
- 13701-13705
- ISSN
- 1433-7851 (ISSN-L)
- 1521-3773
- OpenAlex
- W2137212104
- Cited by
- 467
- References
- 37
- Citations by year
- 2026: 14 · 2025: 22 · 2024: 38 · 2023: 29 · 2022: 47 · 2021: 58 · 2020: 76 · 2019: 72 · 2018: 68 · 2017: 26 · 2016: 16 · 2015: 1
- FWCI
- 10.96
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Angewandte Chemie International Edition (publishedVersion)
- PubMed (publishedVersion)
- Funders
- National Science Foundation (DMR-1006113)
- Office of Naval Research (N00014-15-1-2251)
- UGC India
- Topics
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › CO2 Reduction Techniques and Catalysts
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › Electrocatalysts for Energy Conversion
- Physical Sciences › Chemical Engineering › Catalysis › Catalysts for Methane Reforming
- Keywords
- nitrogen-doped carbon nanotubes, electrochemical CO2 reduction, pyridinic nitrogen, graphitic nitrogen, defect density, CO selectivity, CO2 binding, active site, overpotential, DFT calculations
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
Are you an author, or do you see a problem with this page? Request a review