AI Chat Paper
Note: Please note that the following content is generated by AMiner AI. SciOpen does not take any responsibility related to this content.
{{lang === 'zh_CN' ? '文章概述' : 'Summary'}}
{{lang === 'en_US' ? '中' : 'Eng'}}
Chat more with AI
Powered by AMiner. Clicking this button will take you away from SciOpen.
Home Carbon Future Article
PDF (13.3 MB)
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript AI Chat Paper
Show Outline
Outline
Show full outline
Hide outline
Outline
Show full outline
Hide outline
Research Article | Open Access

Identification of role of nitrogen dopants in nanocarbon catalysis

Xuefei Zhang1,2, Xinying Lin1, Xiaoyan Huang1, Yiquan Chen1, Sen Lin1, Xing Huang1, Zailai Xie1 ( )
Key Laboratory of Advanced Carbon-Based Functional Materials (Fujian Province University), Fuzhou University, Fuzhou 350016, China
College of Chemical Engineering, Fuzhou University, Fuzhou 350016, China
Show Author Information

Graphical Abstract

Two-dimensional nitrogen-doped nanocarbons (NCs) with variable types and contents of nitrogen but constant oxygen species are constructed for oxidative dehydrogenation of ethylbenzene and nitrobenzene hydrogenation reaction. The NC-1000 and NC-850 catalysts exhibit ultra-high catalytic activities, and the active site and nitrogen function mechanism are elucidated by correlating kinetic measurements, structure information, and DFT calculations.

Abstract

The influence of nitrogen dopants on the catalytic activity of carbon-based materials has been studied extensively, but the exact role of nitrogen species in these materials remains unclear. A challenge in understanding the role of nitrogen is that most nitrogen-doped nanocarbon (NC) materials are dominated by uncontrollable surface functional groups, and changes in nitrogen species often lead to variations in oxygen functional groups, which makes the specific role of nitrogen difficult to isolate. To address this issue, we developed a series of NCs containing variable types and contents of nitrogen (5–30 at.%) and a constant oxygen content of approximately 4 at.%. Results show that the different types of nitrogen in the NCs, namely, graphitic nitrogen and pyridinic nitrogen, serve as electron-donating and -withdrawing modulators, respectively, and can tailor the oxidative dehydrogenation activity of the NCs. Additionally, graphitic nitrogen plays a role in mediating frustrated Lewis pairs consisting of pyridinic nitrogen and neighboring carbon atoms. These pairs are responsible for the activation of hydrogen–hydrogen bonds, which is the rate-determining step in nitrobenzene hydrogenation.

Keywords

N-doped carboncharge polarizationactive sitescatalytic mechanismheterogeneous catalysis

Electronic Supplementary Material

Download File(s)
0008_ESM.pdf (3.2 MB)

References

[1]

Zhang, X. F.; Lu, Y. B.; Han, Y. Y.; Feng, R. P.; Xie, Z. L. Unravelling the role of boron dopant in borocarbonitirde catalytic dehydrogenation reaction. J. Energy Chem. 2023, 85, 137–143.
Crossref Google Scholar
[2]

Zhang, X. F.; Dai, X. Y.; Wu, K. H.; Su, B. J.; Chen, J. M.; Qi, W.; Xie, Z. L. A generalized approach to adjust the catalytic activity of borocarbonitride for alkane oxidative dehydrogenation reactions. J. Catal. 2022, 405, 105–115.
Crossref Google Scholar
[3]

Zhang, H. X.; Fan, W. W.; Xia, Q. H.; Yang, H. M. Protein-assisted synthesis of zeolite-supported pseudo-single-atom cobalt catalyst for nitrobenzene hydrogenation. Chem. Eng. J. 2023, 469, 143870.
Crossref Google Scholar
[4]

Luo, Z. C.; Nie, R. F.; Nguyen, V. T.; Biswas, A.; Behera, R. K.; Wu, X.; Kobayashi, T.; Sadow, A.; Wang, B.; Huang, W. Y. et al. Transition metal-like carbocatalyst. Nat. Commun. 2020, 11, 4091.
Crossref Google Scholar
[5]

Ortiz-Medina, J.; Wang, Z. P.; Cruz-Silva, R.; Morelos-Gomez, A.; Wang, F.; Yao, X. D.; Terrones, M.; Endo, M. Defect engineering and surface functionalization of nanocarbons for metal-free catalysis. Adv. Mater. 2019, 31, 1805717.
Crossref Google Scholar
[6]

Yang, N. J.; Zhang, H. Nanocarbon chemistry. Small 2019, 15, 1905367.
Crossref Google Scholar
[7]

Shi, L.; Qi, W.; Liu, W.; Yan, P. Q.; Li, F.; Sun, J. M.; Su, D. S. Carbon nitride modified nanocarbon materials as efficient non-metallic catalysts for alkane dehydrogenation. Catal. Today 2018, 301, 48–54.
Crossref Google Scholar
[8]

Li, G. Z.; Zheng, S. Y.; Wang, L.; Zhang, X. W. Metal-free chemoselective hydrogenation of nitroarenes by N-doped carbon nanotubes via in situ polymerization of pyrrole. ACS Omega 2020, 5, 7519–7528.
Crossref Google Scholar
[9]

Liu, W.; Wang, C.; Herold, F.; Etzold, B. J. M.; Su, D. S.; Qi, W. Oxidative dehydrogenation on nanocarbon: Effect of heteroatom doping. Appl. Catal. B:Environ. 2019, 258, 117982.
Crossref Google Scholar
[10]

Liu, N.; Ding, L. Z.; Li, H. J.; Jia, M. J.; Zhang, W. X.; An, N. H.; Yuan, X. L. N-doped nanoporous carbon as efficient catalyst for nitrobenzene reduction in sulfide-containing aqueous solutions. J. Colloid Interface Sci. 2017, 490, 677–684.
Crossref Google Scholar
[11]

Huang, X. X.; Wu, S. L.; Xiao, Z. C.; Kong, D. B.; Liang, T.; Li, X. L.; Luo, B.; Wang, B.; Zhi, L. J. Predicting the optimal chemical composition of functionalized carbon catalysts towards oxidative dehydrogenation of ethanol to acetaldehyde. Nano Today 2022, 44, 101508.
Crossref Google Scholar
[12]

Hou, Y.; Xia, M.; Han, Y. Y.; Zhang, X. F.; Lu, Y. B.; Yang, Q. H.; Xie, Z. L. Folic acid-derived Low-dimensional carbons for efficient oxidative dehydrogenation of ethylbenzene. J. Colloid Interface Sci. 2023, 638, 291–299.
Crossref Google Scholar
[13]

Zhang, Z.; Yu, L.; Tu, Y. C.; Chen, R. X.; Wu, L. H.; Zhu, J. F.; Deng, D. H. Unveiling the active site of metal-free nitrogen-doped carbon for electrocatalytic carbon dioxide reduction. Cell Rep. Phys. Sci. 2020, 1, 100145.
Crossref Google Scholar
[14]

Lepre, E.; Rat, S.; Cavedon, C.; Seeberger, P. H.; Pieber, B.; Antonietti, M.; López-Salas N. Catalytic properties of high nitrogen content carbonaceous materials. Angew. Chem. , Int. Ed. 2023, 62, e202211663.
Crossref Google Scholar
[15]

Otero, R.; Schöck, M.; Molina, L. M.; Lægsgaard, E.; Stensgaard, I.; Hammer, B.; Besenbacher, F. Guanine quartet networks stabilized by cooperative hydrogen bonds. Angew. Chem. , Int. Ed. 2005, 44, 2270–2275.
Crossref Google Scholar
[16]

Peters, G. M.; Davis, J. T. Supramolecular gels made from nucleobase, nucleoside and nucleotide analogs. Chem. Soc. Rev. 2016, 45, 3188–3206.
Crossref Google Scholar
[17]

Wagner, A.; Upcher, A.; Maria, R.; Magnesen, T.; Zelinger, E.; Raposo, G.; Palmer, B. A. Macromolecular sheets direct the morphology and orientation of plate-like biogenic guanine crystals. Nat. Commun. 2023, 14, 589.
Crossref Google Scholar
[18]

Huang, B. B.; Liu, Y. C.; Xie, Z. L. Two dimensional nanocarbons from biomass and biological molecules: Synthetic strategies and energy related applications. J. Energy Chem. 2021, 54, 795–814.
Crossref Google Scholar
[19]

Huang, B. B.; Liu, Y. C.; Guo, Q.; Fang, Y. X.; Titirici, M. M.; Wang, X. C.; Xie, Z. L. Porous carbon nanosheets from biological nucleobase precursor as efficient pH-independent oxygen reduction electrocatalyst. Carbon 2020, 156, 179–186.
Crossref Google Scholar
[20]

Kossmann, J.; Heil, T.; Antonietti, M.; López-Salas, N. Guanine-derived porous carbonaceous materials: Towards C1N1. ChemSusChem 2020, 13, 6643–6650.
Crossref Google Scholar
[21]

Stefan, L.; Monchaud, D. Applications of guanine quartets in nanotechnology and chemical biology. Nat. Rev. Chem. 2019, 3, 650–668.
Crossref Google Scholar
[22]

Herold, F.; Prosch, S.; Oefner, N.; Brunnengräber, K.; Leubner, O.; Hermans, Y.; Hofmann, K.; Drochner, A.; Hofmann, J. P.; Qi, W. et al. Nanoscale hybrid amorphous/graphitic carbon as key towards next-generation carbon-based oxidative dehydrogenation catalysts. Angew. Chem. , Int. Ed. 2021, 60, 5898–5906.
Crossref Google Scholar
[23]

Um, J.; Yoon, S. U.; Kim, H.; Youn, B. S.; Jin, H. J.; Lim, H. K.; Yun, Y. S. High-performance solid-solution potassium-ion intercalation mechanism of multilayered turbostratic graphene nanosheets. J. Energy Chem. 2022, 67, 814–823.
Crossref Google Scholar
[24]

Zhi, C. Y.; Bando, Y.; Tang, C. C.; Honda, S.; Sato, K.; Kuwahara, H.; Golberg, D. Covalent functionalization: Towards soluble multiwalled boron nitride nanotubes. Angew. Chem. , Int. Ed. 2005, 44, 7932–7935.
Crossref Google Scholar
[25]

Lv, C. D.; Qian, Y. M.; Yan, C. S.; Ding, Y.; Liu, Y. Y.; Chen, G.; Yu, G. H. Defect engineering metal-free polymeric carbon nitride electrocatalyst for effective nitrogen fixation under ambient conditions. Angew. Chem. , Int. Ed. 2018, 57, 10246–10250.
Crossref Google Scholar
[26]

Al-Zahrani, A. A.; Pasupulety, N.; Daous, M. A.; Driss, H.; Ali, A. M.; Zaman, S. F.; Petrov, L. A. Ethyl benzene oxidative dehydrogenation to styrene on Al-B and Al-B-Sb catalysts. Appl. Catal. A:Gen. 2018, 552, 49–57.
Crossref Google Scholar
[27]

Xu, J.; Xue, B.; Liu, Y. M.; Li, Y. X.; Cao, Y.; Fan, K. N. Mesostructured Ni-doped ceria as an efficient catalyst for styrene synthesis by oxidative dehydrogenation of ethylbenzene. Appl. Catal. A:Gen. 2011, 405, 142–148.
Crossref Google Scholar
[28]

Rennard, R. J. Jr.; Innes, R. A.; Swift, H. E. Oxidation over MgCrFeO4 and ZnCrFeO4 catalysts. J. Catal. 1973, 30, 128–138.
Crossref Google Scholar
[29]

Emig, G.; Hofmann, H. Action of zirconium phosphate as a catalyst for the oxydehydrogenation of ethylbenzene to styrene. J. Catal. 1983, 84, 15–26.
Crossref Google Scholar
[30]

Zhang, J.; Su, D. S.; Zhang, A. H.; Wang, D.; Schlögl, R.; Hébert, C. Nanocarbon as robust catalyst: Mechanistic insight into carbon-mediated catalysis. Angew. Chem. , Int. Ed. 2007, 46, 7319–7323.
Crossref Google Scholar
[31]

Shan, J. X.; Sun, X. Q.; Zheng, S. Y.; Wang, T. D.; Zhang, X. W.; Li, G. Z. Graphitic N-dominated nitrogen-doped carbon nanotubes as efficient metal-free catalysts for hydrogenation of nitroarenes. Carbon 2019, 146, 60–69.
Crossref Google Scholar
[32]

Xiong, W.; Wang, Z. N.; He, S. L.; Hao, F.; Yang, Y. Z.; Lv, Y.; Zhang, W. B.; Liu, P. L.; Luo, H. Nitrogen-doped carbon nanotubes as a highly active metal-free catalyst for nitrobenzene hydrogenation. Appl. Catal. B:Environ. 2020, 260, 118105.
Crossref Google Scholar
[33]

Xu, F.; Zhai, Y. X.; Zhang, E.; Liu, Q. H.; Jiang, G. S.; Xu, X. S.; Qiu, Y. Q.; Liu, X. M.; Wang, H. Q.; Kaskel, S. Ultrastable surface-dominated pseudocapacitive potassium storage enabled by edge-enriched N-doped porous carbon nanosheets. Angew. Chem. , Int. Ed. 2020, 59, 19460–19467.
Crossref Google Scholar
[34]

Zhang, X. F.; Yan, P. Q.; Xu, J. K.; Li, F.; Herold, F.; Etzold, B. J. M.; Wang, P.; Su, D. S.; Lin, S.; Qi, W. et al. Methanol conversion on borocarbonitride catalysts: Identification and quantification of active sites. Sci. Adv. 2020, 6, eaba5778.
Crossref Google Scholar
[35]

Ou, H. H.; Lin, L. H.; Zheng, Y.; Yang, P. J.; Fang, Y. X.; Wang, X. C. Tri-s-triazine-based crystalline carbon nitride nanosheets for an improved hydrogen evolution. Adv. Mater. 2017, 29, 1700008.
Crossref Google Scholar
[36]

Qi, W.; Liu, W.; Guo, X. L.; Schlögl, R.; Su, D. S. Oxidative dehydrogenation on nanocarbon: Intrinsic catalytic activity and structure-function relationships. Angew. Chem. , Int. Ed. 2015, 54, 13682–13685.
Crossref Google Scholar
[37]

Frank, B.; Zhang, J.; Blume, R.; Schlögl, R.; Su, D. S. Heteroatoms increase the selectivity in oxidative dehydrogenation reactions on nanocarbons. Angew. Chem. , Int. Ed. 2009, 48, 6913–6917.
Crossref Google Scholar
[38]

Chen, D. J.; Wang, Y. T.; Klankermayer, J. Enantioselective hydrogenation with chiral frustrated Lewis pairs. Angew. Chem. , Int. Ed. 2010, 49, 9475–9478.
Crossref Google Scholar
[39]

Stephan, D. W. Frustrated Lewis pairs. J. Am. Chem. Soc. 2015, 137, 10018–10032.
Crossref Google Scholar
[40]

Liu, L.; Cao, L. L.; Shao, Y.; Ménard, G.; Stephan, D. W. A radical mechanism for frustrated Lewis pair reactivity. Chem 2017, 3, 259–267.
Crossref Google Scholar
[41]

Wan, Q.; Chen, Y.; Zhou, S. L.; Lin, J.; Lin, S. Selective hydrogenation of acetylene to ethylene on anatase TiO2 through first-principles studies. J. Mater. Chem. A 2021, 9, 14064–14073.
Crossref Google Scholar
[42]

Huang, X. Y.; Zeng, X. H.; Zhang, X. F.; Xie, Z. L. Carbon-based frustrated Lewis pairs mediate hydrogenation. Phys. Chem. Chem. Phys. 2022, 24, 28895–28902.
Crossref Google Scholar
[43]

Liao, C. J.; Liu, B.; Chi, Q.; Zhang, Z. H. Nitrogen-doped carbon materials for the metal-free reduction of nitro compounds. ACS Appl. Mater. Interfaces 2018, 10, 44421–44429.
Crossref Google Scholar
[44]

Kresse, G.; Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 1996, 6, 15–50.
Crossref Google Scholar
[45]

Kresse, G.; Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 1996, 54, 11169–11186.
Crossref Google Scholar
[46]

Kresse, G.; Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 1999, 59, 1758–1775.
Crossref Google Scholar
[47]

Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 1994, 50, 17953–17979.
Crossref Google Scholar
[48]

Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 2010, 132, 154104.
Crossref Google Scholar
[49]

Henkelman, G.; Uberuaga, B. P.; Jónsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 2000, 113, 9901–9904.
Crossref Google Scholar
[50]
Henkelman, G.; Jónsson, H. A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives. J. Chem. Phys. 1999, 111, 7010–7022.
Crossref
[51]

Olsen, R. A.; Kroes, G. J.; Henkelman, G.; Arnaldsson, A.; Jónsson, H. Comparison of methods for finding saddle points without knowledge of the final states. J. Chem. Phys. 2004, 121, 9776–9792.
Crossref Google Scholar
[52]

Heyden, A.; Bell, A. T.; Keil, F. J. Efficient methods for finding transition states in chemical reactions: Comparison of improved dimer method and partitioned rational function optimization method. J. Chem. Phys. 2005, 123, 224101.
Crossref Google Scholar
Carbon Future
Volume 1 Issue 2,
June 2024
Article number: 9200008
DOI: 10.26599/CF.2024.9200008
Cite this article:
Zhang X, Lin X, Huang X, et al. Identification of role of nitrogen dopants in nanocarbon catalysis. Carbon Future, 2024, 1(2): 9200008. https://doi.org/10.26599/CF.2024.9200008
Part of a topical collection:
Sustainable carbon materials for innovative catalysis

3211

Views

612

Downloads

6

Crossref

Altmetrics
Received: 14 November 2023
Revised: 14 December 2023
Accepted: 30 December 2023
Published: 04 February 2024
© The Author(s) 2024.

Open Access This article is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0), which permits reusers to distribute, remix, adapt, and build upon the material in any medium or format, so long as attribution is given to the original author(s) and the source, provide a link to the license, and indicate if changes were made. See https://creativecommons.org/licenses/by/4.0/.
Return