Yueling Chen, Mingfei Yu, Guocheng Huang, Qiaoshan Chen, Jinhong Bi
{"title":"石墨化氮化碳层间电荷转移实现高效光催化固氮","authors":"Yueling Chen, Mingfei Yu, Guocheng Huang, Qiaoshan Chen, Jinhong Bi","doi":"10.1002/smll.202205388","DOIUrl":null,"url":null,"abstract":"<p>Exploiting cost-effective, high-efficiency, and contamination-free semiconductors for photocatalytic nitrogen reduction reaction (N<sub>2</sub>RR) is still a great challenge, especially in sacrificial-free system. On basis of the electron “acceptance–donation” concept, a boron-doped and carbon-deficient <i>g</i>-C<sub>3</sub>N<sub>4</sub> (B<sub>x</sub>CvN) is herein developed through precise dopant and defect engineering. The optimized B<sub>15</sub>CvN exhibisted an NH<sub>3</sub> production rate of 135.3 µmol h<sup>−1</sup> g<sup>−1</sup> in pure water with nine-fold enhancement to the pristine graphitic carbon nitride (<i>g</i>-C<sub>3</sub>N<sub>4</sub>), on account of the markedly elevated visible-light harvesting, N<sub>2</sub> activation, and multi-directional photoinduced carriers transfer. The decorated B atoms with coexistent occupied and empty sp<sup>3</sup> hybridized orbitals are theoretically proved to be in charge of the increase of N<sub>2</sub> adsorption energy from –0.08 to –0.26 eV and the change in N<sub>2</sub> adsorption model from one-way to two-way end-on pattern. Noticeably, the elaborate coordination of doped B atoms and carbon vacancies greatly facilitated the interlayer interaction and vertical charge migration of B<sub>x</sub>CvN, which is distinctly revealed through the charge density difference calculations. The current study provides an alternative groundbreaking perspective for advancing photocatalytic N<sub>2</sub>RR through the targeted configuration of the defect and dopant sites.</p>","PeriodicalId":228,"journal":{"name":"Small","volume":null,"pages":null},"PeriodicalIF":13.0000,"publicationDate":"2022-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"4","resultStr":"{\"title\":\"Interlayer Charge Transfer Over Graphitized Carbon Nitride Enabling Highly-Efficient Photocatalytic Nitrogen Fixation\",\"authors\":\"Yueling Chen, Mingfei Yu, Guocheng Huang, Qiaoshan Chen, Jinhong Bi\",\"doi\":\"10.1002/smll.202205388\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Exploiting cost-effective, high-efficiency, and contamination-free semiconductors for photocatalytic nitrogen reduction reaction (N<sub>2</sub>RR) is still a great challenge, especially in sacrificial-free system. On basis of the electron “acceptance–donation” concept, a boron-doped and carbon-deficient <i>g</i>-C<sub>3</sub>N<sub>4</sub> (B<sub>x</sub>CvN) is herein developed through precise dopant and defect engineering. The optimized B<sub>15</sub>CvN exhibisted an NH<sub>3</sub> production rate of 135.3 µmol h<sup>−1</sup> g<sup>−1</sup> in pure water with nine-fold enhancement to the pristine graphitic carbon nitride (<i>g</i>-C<sub>3</sub>N<sub>4</sub>), on account of the markedly elevated visible-light harvesting, N<sub>2</sub> activation, and multi-directional photoinduced carriers transfer. The decorated B atoms with coexistent occupied and empty sp<sup>3</sup> hybridized orbitals are theoretically proved to be in charge of the increase of N<sub>2</sub> adsorption energy from –0.08 to –0.26 eV and the change in N<sub>2</sub> adsorption model from one-way to two-way end-on pattern. Noticeably, the elaborate coordination of doped B atoms and carbon vacancies greatly facilitated the interlayer interaction and vertical charge migration of B<sub>x</sub>CvN, which is distinctly revealed through the charge density difference calculations. The current study provides an alternative groundbreaking perspective for advancing photocatalytic N<sub>2</sub>RR through the targeted configuration of the defect and dopant sites.</p>\",\"PeriodicalId\":228,\"journal\":{\"name\":\"Small\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":13.0000,\"publicationDate\":\"2022-11-07\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"4\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Small\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/smll.202205388\",\"RegionNum\":2,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Small","FirstCategoryId":"88","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/smll.202205388","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Interlayer Charge Transfer Over Graphitized Carbon Nitride Enabling Highly-Efficient Photocatalytic Nitrogen Fixation
Exploiting cost-effective, high-efficiency, and contamination-free semiconductors for photocatalytic nitrogen reduction reaction (N2RR) is still a great challenge, especially in sacrificial-free system. On basis of the electron “acceptance–donation” concept, a boron-doped and carbon-deficient g-C3N4 (BxCvN) is herein developed through precise dopant and defect engineering. The optimized B15CvN exhibisted an NH3 production rate of 135.3 µmol h−1 g−1 in pure water with nine-fold enhancement to the pristine graphitic carbon nitride (g-C3N4), on account of the markedly elevated visible-light harvesting, N2 activation, and multi-directional photoinduced carriers transfer. The decorated B atoms with coexistent occupied and empty sp3 hybridized orbitals are theoretically proved to be in charge of the increase of N2 adsorption energy from –0.08 to –0.26 eV and the change in N2 adsorption model from one-way to two-way end-on pattern. Noticeably, the elaborate coordination of doped B atoms and carbon vacancies greatly facilitated the interlayer interaction and vertical charge migration of BxCvN, which is distinctly revealed through the charge density difference calculations. The current study provides an alternative groundbreaking perspective for advancing photocatalytic N2RR through the targeted configuration of the defect and dopant sites.
期刊介绍:
Small serves as an exceptional platform for both experimental and theoretical studies in fundamental and applied interdisciplinary research at the nano- and microscale. The journal offers a compelling mix of peer-reviewed Research Articles, Reviews, Perspectives, and Comments.
With a remarkable 2022 Journal Impact Factor of 13.3 (Journal Citation Reports from Clarivate Analytics, 2023), Small remains among the top multidisciplinary journals, covering a wide range of topics at the interface of materials science, chemistry, physics, engineering, medicine, and biology.
Small's readership includes biochemists, biologists, biomedical scientists, chemists, engineers, information technologists, materials scientists, physicists, and theoreticians alike.