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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
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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

heterogeneous catalysisN-doped carboncharge polarizationcatalytic mechanismactive sites

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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
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Sustainable carbon materials for innovative catalysis

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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/.
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