{"title":"通过掺杂锰的 g-C3N4 中 Mn3+ 的 π 背负过程实现有效的电化学氮还原","authors":"Yijin Ma, Yinpeng Lu, Chang Li, Liangqing Hu, Hexin Zhang, Jing Feng","doi":"10.1007/s10562-024-04772-1","DOIUrl":null,"url":null,"abstract":"<div><p>Ammonia (NH<sub>3</sub>) synthesis via nitrogen reduction reaction under mild conditions is challenging due to the difficulty of activating nitrogen. Herein, Mn-doped g-C<sub>3</sub>N<sub>4</sub> (x-Mn-CN, x = 5, 10, and 15) catalysts with efficiency NRR performance were synthesized. The resulting 5-Mn-CN exhibits higher NRR performance (NH<sub>3</sub> yield rate: 15.2 μg h<sup>−1</sup> mg<sub>cat</sub><sup>−1</sup>, Faradaic efficiency: 7.1%) at -0.4 V (<i>vs. RHE</i>) than others. It is found that the active sites of Mn<sup>3+</sup> are generated by electron transfer from Mn<sup>2+</sup> to the N of g-C<sub>3</sub>N<sub>4,</sub> and active N<sub>2</sub> through the π back-donation process. This is evidenced by the experimental result that the NH<sub>3</sub> yield rate of 5-Mn-CN significantly decreases from 15.2 μg h<sup>−1</sup> mg<sub>cat</sub><sup>−1</sup> to 2.6 μg h<sup>−1</sup> mg<sub>cat</sub><sup>−1</sup> after lowering the concentration of Mn<sup>3+</sup>. The concentration of Mn<sup>3+</sup> is reduced by treating the catalyst in the ethylenediaminetetraacetic acid disodium salt (EDTA-2Na) solution. This study enhances the understanding of N<sub>2</sub> activation and provides insights into the transition metal-doped g-C<sub>3</sub>N<sub>4</sub> as NRR catalysts.</p><h3>Graphical Abstract</h3>\n<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"154 11","pages":"5830 - 5837"},"PeriodicalIF":2.3000,"publicationDate":"2024-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Effective Electrochemical Nitrogen Reduction through π Back-donation Process in Mn3+ of Mn-doped g-C3N4\",\"authors\":\"Yijin Ma, Yinpeng Lu, Chang Li, Liangqing Hu, Hexin Zhang, Jing Feng\",\"doi\":\"10.1007/s10562-024-04772-1\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Ammonia (NH<sub>3</sub>) synthesis via nitrogen reduction reaction under mild conditions is challenging due to the difficulty of activating nitrogen. Herein, Mn-doped g-C<sub>3</sub>N<sub>4</sub> (x-Mn-CN, x = 5, 10, and 15) catalysts with efficiency NRR performance were synthesized. The resulting 5-Mn-CN exhibits higher NRR performance (NH<sub>3</sub> yield rate: 15.2 μg h<sup>−1</sup> mg<sub>cat</sub><sup>−1</sup>, Faradaic efficiency: 7.1%) at -0.4 V (<i>vs. RHE</i>) than others. It is found that the active sites of Mn<sup>3+</sup> are generated by electron transfer from Mn<sup>2+</sup> to the N of g-C<sub>3</sub>N<sub>4,</sub> and active N<sub>2</sub> through the π back-donation process. This is evidenced by the experimental result that the NH<sub>3</sub> yield rate of 5-Mn-CN significantly decreases from 15.2 μg h<sup>−1</sup> mg<sub>cat</sub><sup>−1</sup> to 2.6 μg h<sup>−1</sup> mg<sub>cat</sub><sup>−1</sup> after lowering the concentration of Mn<sup>3+</sup>. The concentration of Mn<sup>3+</sup> is reduced by treating the catalyst in the ethylenediaminetetraacetic acid disodium salt (EDTA-2Na) solution. This study enhances the understanding of N<sub>2</sub> activation and provides insights into the transition metal-doped g-C<sub>3</sub>N<sub>4</sub> as NRR catalysts.</p><h3>Graphical Abstract</h3>\\n<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>\",\"PeriodicalId\":508,\"journal\":{\"name\":\"Catalysis Letters\",\"volume\":\"154 11\",\"pages\":\"5830 - 5837\"},\"PeriodicalIF\":2.3000,\"publicationDate\":\"2024-07-08\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Catalysis Letters\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s10562-024-04772-1\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Catalysis Letters","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s10562-024-04772-1","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Effective Electrochemical Nitrogen Reduction through π Back-donation Process in Mn3+ of Mn-doped g-C3N4
Ammonia (NH3) synthesis via nitrogen reduction reaction under mild conditions is challenging due to the difficulty of activating nitrogen. Herein, Mn-doped g-C3N4 (x-Mn-CN, x = 5, 10, and 15) catalysts with efficiency NRR performance were synthesized. The resulting 5-Mn-CN exhibits higher NRR performance (NH3 yield rate: 15.2 μg h−1 mgcat−1, Faradaic efficiency: 7.1%) at -0.4 V (vs. RHE) than others. It is found that the active sites of Mn3+ are generated by electron transfer from Mn2+ to the N of g-C3N4, and active N2 through the π back-donation process. This is evidenced by the experimental result that the NH3 yield rate of 5-Mn-CN significantly decreases from 15.2 μg h−1 mgcat−1 to 2.6 μg h−1 mgcat−1 after lowering the concentration of Mn3+. The concentration of Mn3+ is reduced by treating the catalyst in the ethylenediaminetetraacetic acid disodium salt (EDTA-2Na) solution. This study enhances the understanding of N2 activation and provides insights into the transition metal-doped g-C3N4 as NRR catalysts.
期刊介绍:
Catalysis Letters aim is the rapid publication of outstanding and high-impact original research articles in catalysis. The scope of the journal covers a broad range of topics in all fields of both applied and theoretical catalysis, including heterogeneous, homogeneous and biocatalysis.
The high-quality original research articles published in Catalysis Letters are subject to rigorous peer review. Accepted papers are published online first and subsequently in print issues. All contributions must include a graphical abstract. Manuscripts should be written in English and the responsibility lies with the authors to ensure that they are grammatically and linguistically correct. Authors for whom English is not the working language are encouraged to consider using a professional language-editing service before submitting their manuscripts.