Modulation of electronic structure of metal-free graphdiyne via precise nitrogen modification for oxygen evolution reaction
The oxygen evolution reaction (OER) is essential for energy conversion and storage but is hindered by sluggish kinetics, low efficiency, and high overpotentials. Although RuO₂ and IrO₂ are efficient catalysts, their high cost and scarcity limit their large-scale application. In contrast, nonmetallic...
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KeAi Communications Co., Ltd.
2025-08-01
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| Series: | ChemPhysMater |
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| author | Mei Wang Xinliang Fu Mengyu Lu Guodong Shi Xiufan Liu Mingjian Yuan |
| author_facet | Mei Wang Xinliang Fu Mengyu Lu Guodong Shi Xiufan Liu Mingjian Yuan |
| author_sort | Mei Wang |
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| description | The oxygen evolution reaction (OER) is essential for energy conversion and storage but is hindered by sluggish kinetics, low efficiency, and high overpotentials. Although RuO₂ and IrO₂ are efficient catalysts, their high cost and scarcity limit their large-scale application. In contrast, nonmetallic catalysts have gained traction as promising alternatives due to their cost-effectiveness, high stability, and environmental sustainability. The OER efficiency depends on optimal adsorption/desorption of oxygen intermediates, such as *O, OH*, and OOH*, on the catalyst surface. The electronic structure of carbon materials can be optimized via nitrogen doping, which introduces a higher polarity than carbon atoms, thereby optimizing the adsorption free energy of oxygen species during an OER. However, conventional high-temperature pyrolysis methods suffer from limitations such as inaccuracy and high energy consumption. The unique and facile bottom-up synthesis of graphdiyne (GDY) enables precise control over the doping positions of the three sp²-N atoms in GDY (1NGDY, 2NGDY, and 3NGDY) via monomer design engineering. By integrating density functional theory (DFT) calculations with experimental validation, we tailored the adsorption free energy of the oxygen intermediates in the OER, thereby optimizing the rate-determining step of *OOH generation. Among these three kinds of nitrogen-doped GDY catalysts, 3NGDY which incorporates three sp2-N atoms exhibited the optimal electrocatalytic performance, achieving a current density of 10 mA cm⁻² in 1 M KOH with a low overpotential of approximately 310 mV. This study demonstrates the significant potential of GDY-based metal-free catalysts in the development of cost-effective, high-performance electrocatalysts. |
| format | Article |
| id | doaj-art-99f077c0622e4fbe84a2dfd709261b48 |
| institution | Kabale University |
| issn | 2772-5715 |
| language | English |
| publishDate | 2025-08-01 |
| publisher | KeAi Communications Co., Ltd. |
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| series | ChemPhysMater |
| spelling | doaj-art-99f077c0622e4fbe84a2dfd709261b482025-08-20T03:25:29ZengKeAi Communications Co., Ltd.ChemPhysMater2772-57152025-08-014328929510.1016/j.chphma.2025.02.003Modulation of electronic structure of metal-free graphdiyne via precise nitrogen modification for oxygen evolution reactionMei Wang0Xinliang Fu1Mengyu Lu2Guodong Shi3Xiufan Liu4Mingjian Yuan5School of Materials Science and Engineering, Institute for New Energy Materials & Low Carbon Technologies, Tianjin University of Technology, Tianjin 300384, China; Corresponding authors.Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, Tianjin 300071, China; Hubei Key Laboratory of Pollutant Analysis & Reuse Technology, College of Chemistry and Chemical Engineering, Hubei Normal University, Huangshi 435002, ChinaSchool of Materials Science and Engineering, Institute for New Energy Materials & Low Carbon Technologies, Tianjin University of Technology, Tianjin 300384, ChinaCollege of Science, Henan University of Technology, Zhengzhou 450001, ChinaHubei Key Laboratory of Pollutant Analysis & Reuse Technology, College of Chemistry and Chemical Engineering, Hubei Normal University, Huangshi 435002, China; Corresponding authors.Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, Tianjin 300071, China; Corresponding authors.The oxygen evolution reaction (OER) is essential for energy conversion and storage but is hindered by sluggish kinetics, low efficiency, and high overpotentials. Although RuO₂ and IrO₂ are efficient catalysts, their high cost and scarcity limit their large-scale application. In contrast, nonmetallic catalysts have gained traction as promising alternatives due to their cost-effectiveness, high stability, and environmental sustainability. The OER efficiency depends on optimal adsorption/desorption of oxygen intermediates, such as *O, OH*, and OOH*, on the catalyst surface. The electronic structure of carbon materials can be optimized via nitrogen doping, which introduces a higher polarity than carbon atoms, thereby optimizing the adsorption free energy of oxygen species during an OER. However, conventional high-temperature pyrolysis methods suffer from limitations such as inaccuracy and high energy consumption. The unique and facile bottom-up synthesis of graphdiyne (GDY) enables precise control over the doping positions of the three sp²-N atoms in GDY (1NGDY, 2NGDY, and 3NGDY) via monomer design engineering. By integrating density functional theory (DFT) calculations with experimental validation, we tailored the adsorption free energy of the oxygen intermediates in the OER, thereby optimizing the rate-determining step of *OOH generation. Among these three kinds of nitrogen-doped GDY catalysts, 3NGDY which incorporates three sp2-N atoms exhibited the optimal electrocatalytic performance, achieving a current density of 10 mA cm⁻² in 1 M KOH with a low overpotential of approximately 310 mV. This study demonstrates the significant potential of GDY-based metal-free catalysts in the development of cost-effective, high-performance electrocatalysts.http://www.sciencedirect.com/science/article/pii/S2772571525000154Oxygen evolution reactionGraphdiyneMetal-free catalystsN-doping graphdiyne |
| spellingShingle | Mei Wang Xinliang Fu Mengyu Lu Guodong Shi Xiufan Liu Mingjian Yuan Modulation of electronic structure of metal-free graphdiyne via precise nitrogen modification for oxygen evolution reaction ChemPhysMater Oxygen evolution reaction Graphdiyne Metal-free catalysts N-doping graphdiyne |
| title | Modulation of electronic structure of metal-free graphdiyne via precise nitrogen modification for oxygen evolution reaction |
| title_full | Modulation of electronic structure of metal-free graphdiyne via precise nitrogen modification for oxygen evolution reaction |
| title_fullStr | Modulation of electronic structure of metal-free graphdiyne via precise nitrogen modification for oxygen evolution reaction |
| title_full_unstemmed | Modulation of electronic structure of metal-free graphdiyne via precise nitrogen modification for oxygen evolution reaction |
| title_short | Modulation of electronic structure of metal-free graphdiyne via precise nitrogen modification for oxygen evolution reaction |
| title_sort | modulation of electronic structure of metal free graphdiyne via precise nitrogen modification for oxygen evolution reaction |
| topic | Oxygen evolution reaction Graphdiyne Metal-free catalysts N-doping graphdiyne |
| url | http://www.sciencedirect.com/science/article/pii/S2772571525000154 |
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