Xuefei Zhang , Yanbing Lu , Yingyi Han , Runping Feng , Zailai Xie
{"title":"硼掺杂剂在硼碳酸酯催化脱氢反应中的作用","authors":"Xuefei Zhang , Yanbing Lu , Yingyi Han , Runping Feng , Zailai Xie","doi":"10.1016/j.jechem.2023.05.039","DOIUrl":null,"url":null,"abstract":"<div><p>Borocarbonitride (BCN) materials are newly developed metal-free catalytic materials exhibiting high selectivity in oxidative dehydrogenation (ODH) of alkanes. However, the in-depth understandings on the role of boron (B) dopants and the intrinsic activities of –C=O and –B–OH still remain unknown. Herein, we report a series of BCN materials with regulable B content and surface oxygen functional groups via self-assembly and pyrolysis of guanine and boric acid. We found that the B/C ratio is the key parameter to determine the activity of ODH and product distribution. Among them, the high ethylbenzene conversion (∼57%) and styrene selectivity (∼83%) are achieved in ODH for B<sub>1</sub>CN. The styrene selectivity can be improved by increasing of B/C ratio and this value reaches near 100% for B<sub>5</sub>CN. Structural characterizations and kinetic measurements indicate that –C=O and –B–OH dual sites on BCN are real active sites of ODH reaction. The intrinsic activity of –C=O (5.556 × 10<sup>−4</sup> s<sup>−1</sup>) is found to be 23.7 times higher than –B–OH (0.234 × 10<sup>−4</sup> s<sup>−1</sup>) site. More importantly, we reveal that the deep oxidation to undesirable CO<sub>2</sub> occurs on –C=O rather than –B–OH site, and B dopant in BCN materials can reduce the nucleophilicity of –C=O site to eliminate the CO<sub>2</sub> emission. Overall, the present work provides a new insight on the structure–function relationship of the BCN catalytic systems.</p></div>","PeriodicalId":67498,"journal":{"name":"能源化学","volume":null,"pages":null},"PeriodicalIF":14.0000,"publicationDate":"2023-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"1","resultStr":"{\"title\":\"Unravelling the role of boron dopant in borocarbonitirde catalytic dehydrogenation reaction\",\"authors\":\"Xuefei Zhang , Yanbing Lu , Yingyi Han , Runping Feng , Zailai Xie\",\"doi\":\"10.1016/j.jechem.2023.05.039\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Borocarbonitride (BCN) materials are newly developed metal-free catalytic materials exhibiting high selectivity in oxidative dehydrogenation (ODH) of alkanes. However, the in-depth understandings on the role of boron (B) dopants and the intrinsic activities of –C=O and –B–OH still remain unknown. Herein, we report a series of BCN materials with regulable B content and surface oxygen functional groups via self-assembly and pyrolysis of guanine and boric acid. We found that the B/C ratio is the key parameter to determine the activity of ODH and product distribution. Among them, the high ethylbenzene conversion (∼57%) and styrene selectivity (∼83%) are achieved in ODH for B<sub>1</sub>CN. The styrene selectivity can be improved by increasing of B/C ratio and this value reaches near 100% for B<sub>5</sub>CN. Structural characterizations and kinetic measurements indicate that –C=O and –B–OH dual sites on BCN are real active sites of ODH reaction. The intrinsic activity of –C=O (5.556 × 10<sup>−4</sup> s<sup>−1</sup>) is found to be 23.7 times higher than –B–OH (0.234 × 10<sup>−4</sup> s<sup>−1</sup>) site. More importantly, we reveal that the deep oxidation to undesirable CO<sub>2</sub> occurs on –C=O rather than –B–OH site, and B dopant in BCN materials can reduce the nucleophilicity of –C=O site to eliminate the CO<sub>2</sub> emission. Overall, the present work provides a new insight on the structure–function relationship of the BCN catalytic systems.</p></div>\",\"PeriodicalId\":67498,\"journal\":{\"name\":\"能源化学\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":14.0000,\"publicationDate\":\"2023-10-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"1\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"能源化学\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S209549562300325X\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, APPLIED\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"能源化学","FirstCategoryId":"1085","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S209549562300325X","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
Unravelling the role of boron dopant in borocarbonitirde catalytic dehydrogenation reaction
Borocarbonitride (BCN) materials are newly developed metal-free catalytic materials exhibiting high selectivity in oxidative dehydrogenation (ODH) of alkanes. However, the in-depth understandings on the role of boron (B) dopants and the intrinsic activities of –C=O and –B–OH still remain unknown. Herein, we report a series of BCN materials with regulable B content and surface oxygen functional groups via self-assembly and pyrolysis of guanine and boric acid. We found that the B/C ratio is the key parameter to determine the activity of ODH and product distribution. Among them, the high ethylbenzene conversion (∼57%) and styrene selectivity (∼83%) are achieved in ODH for B1CN. The styrene selectivity can be improved by increasing of B/C ratio and this value reaches near 100% for B5CN. Structural characterizations and kinetic measurements indicate that –C=O and –B–OH dual sites on BCN are real active sites of ODH reaction. The intrinsic activity of –C=O (5.556 × 10−4 s−1) is found to be 23.7 times higher than –B–OH (0.234 × 10−4 s−1) site. More importantly, we reveal that the deep oxidation to undesirable CO2 occurs on –C=O rather than –B–OH site, and B dopant in BCN materials can reduce the nucleophilicity of –C=O site to eliminate the CO2 emission. Overall, the present work provides a new insight on the structure–function relationship of the BCN catalytic systems.