Investigation on the Edge Doping Process of Nitrogen-Doped Carbon Materials by In Situ Pyrolysis Mass Spectrometry and Laser-Induced Acoustic Desorption Mass Spectrometry
Nitrogen-doped carbon materials demonstrate high performance as electrodes in fuel cells and higher oxygen reduction reactivity than traditional Pt-based electrodes. However, the formation process of nitrogen-doped carbon materials has long been a mystery. In this study, the formation mechanism of n...
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MDPI AG
2023-04-01
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| Online Access: | https://www.mdpi.com/2073-4344/13/5/830 |
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| author | Yihuang Jiang Zaifa Shi Qingjie Zeng Jiangle Zhang Zefeng Deng Qiaolin Wang Jing Yang Jingxiong Yu Zhengbo Qin Zichao Tang |
| author_facet | Yihuang Jiang Zaifa Shi Qingjie Zeng Jiangle Zhang Zefeng Deng Qiaolin Wang Jing Yang Jingxiong Yu Zhengbo Qin Zichao Tang |
| author_sort | Yihuang Jiang |
| collection | DOAJ |
| description | Nitrogen-doped carbon materials demonstrate high performance as electrodes in fuel cells and higher oxygen reduction reactivity than traditional Pt-based electrodes. However, the formation process of nitrogen-doped carbon materials has long been a mystery. In this study, the formation mechanism of nitrogen-doped carbon materials from polyaniline (PANI) pyrolysis was studied by the combination of in situ pyrolysis vacuum ultraviolet photoionization time-of-flight mass spectrometry (Py-VUVPI-TOF MS) and substrate-enhanced, laser-induced acoustic desorption source time-of-flight mass spectrometry (SE-LIAD-TOF MS). The initial pyrolysis species, including free radicals and intermediates, were investigated via in situ Py-VUVPI-TOF MS during the temperature-programmed desorption process (within tens of microseconds). The pyrolysis residues were collected and further investigated via SE-LIAD-TOF MS, revealing the product information of the initial pyrolysis products. The results show that the edge doping of carbon materials depends on free radical reactions rather than the direct substitution of carbon atoms by nitrogen atoms. Meanwhile, pyrrole nitrogen and pyridine nitrogen are formed by the free radical cyclization reaction and the amino aromatization reaction at the initial stage of pyrolysis, while the formation of graphitic nitrogen depends on the further polymerization reaction of pyrrole nitrogen and pyridine nitrogen. |
| first_indexed | 2024-03-11T03:52:11Z |
| format | Article |
| id | doaj.art-dc39232364544935a156208cb177d9dc |
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| issn | 2073-4344 |
| language | English |
| last_indexed | 2024-03-11T03:52:11Z |
| publishDate | 2023-04-01 |
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| record_format | Article |
| series | Catalysts |
| spelling | doaj.art-dc39232364544935a156208cb177d9dc2023-11-18T00:50:48ZengMDPI AGCatalysts2073-43442023-04-0113583010.3390/catal13050830Investigation on the Edge Doping Process of Nitrogen-Doped Carbon Materials by In Situ Pyrolysis Mass Spectrometry and Laser-Induced Acoustic Desorption Mass SpectrometryYihuang Jiang0Zaifa Shi1Qingjie Zeng2Jiangle Zhang3Zefeng Deng4Qiaolin Wang5Jing Yang6Jingxiong Yu7Zhengbo Qin8Zichao Tang9State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, ChinaState Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, ChinaState Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, ChinaState Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, ChinaState Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, ChinaAnhui Province Key Laboratory of Optoelectric Materials Science and Technology, School of Physics and Electronic Information, Anhui Normal University, Wuhu 241002, ChinaState Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, ChinaKey Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800, ChinaAnhui Province Key Laboratory of Optoelectric Materials Science and Technology, School of Physics and Electronic Information, Anhui Normal University, Wuhu 241002, ChinaState Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, ChinaNitrogen-doped carbon materials demonstrate high performance as electrodes in fuel cells and higher oxygen reduction reactivity than traditional Pt-based electrodes. However, the formation process of nitrogen-doped carbon materials has long been a mystery. In this study, the formation mechanism of nitrogen-doped carbon materials from polyaniline (PANI) pyrolysis was studied by the combination of in situ pyrolysis vacuum ultraviolet photoionization time-of-flight mass spectrometry (Py-VUVPI-TOF MS) and substrate-enhanced, laser-induced acoustic desorption source time-of-flight mass spectrometry (SE-LIAD-TOF MS). The initial pyrolysis species, including free radicals and intermediates, were investigated via in situ Py-VUVPI-TOF MS during the temperature-programmed desorption process (within tens of microseconds). The pyrolysis residues were collected and further investigated via SE-LIAD-TOF MS, revealing the product information of the initial pyrolysis products. The results show that the edge doping of carbon materials depends on free radical reactions rather than the direct substitution of carbon atoms by nitrogen atoms. Meanwhile, pyrrole nitrogen and pyridine nitrogen are formed by the free radical cyclization reaction and the amino aromatization reaction at the initial stage of pyrolysis, while the formation of graphitic nitrogen depends on the further polymerization reaction of pyrrole nitrogen and pyridine nitrogen.https://www.mdpi.com/2073-4344/13/5/830nitrogen-doped carbon materialspolyanilinein situ pyrolysisvacuum ultraviolet photoionizationlaser-induced acoustic desorption |
| spellingShingle | Yihuang Jiang Zaifa Shi Qingjie Zeng Jiangle Zhang Zefeng Deng Qiaolin Wang Jing Yang Jingxiong Yu Zhengbo Qin Zichao Tang Investigation on the Edge Doping Process of Nitrogen-Doped Carbon Materials by In Situ Pyrolysis Mass Spectrometry and Laser-Induced Acoustic Desorption Mass Spectrometry Catalysts nitrogen-doped carbon materials polyaniline in situ pyrolysis vacuum ultraviolet photoionization laser-induced acoustic desorption |
| title | Investigation on the Edge Doping Process of Nitrogen-Doped Carbon Materials by In Situ Pyrolysis Mass Spectrometry and Laser-Induced Acoustic Desorption Mass Spectrometry |
| title_full | Investigation on the Edge Doping Process of Nitrogen-Doped Carbon Materials by In Situ Pyrolysis Mass Spectrometry and Laser-Induced Acoustic Desorption Mass Spectrometry |
| title_fullStr | Investigation on the Edge Doping Process of Nitrogen-Doped Carbon Materials by In Situ Pyrolysis Mass Spectrometry and Laser-Induced Acoustic Desorption Mass Spectrometry |
| title_full_unstemmed | Investigation on the Edge Doping Process of Nitrogen-Doped Carbon Materials by In Situ Pyrolysis Mass Spectrometry and Laser-Induced Acoustic Desorption Mass Spectrometry |
| title_short | Investigation on the Edge Doping Process of Nitrogen-Doped Carbon Materials by In Situ Pyrolysis Mass Spectrometry and Laser-Induced Acoustic Desorption Mass Spectrometry |
| title_sort | investigation on the edge doping process of nitrogen doped carbon materials by in situ pyrolysis mass spectrometry and laser induced acoustic desorption mass spectrometry |
| topic | nitrogen-doped carbon materials polyaniline in situ pyrolysis vacuum ultraviolet photoionization laser-induced acoustic desorption |
| url | https://www.mdpi.com/2073-4344/13/5/830 |
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