Gian Marco Beshara, Ivan Surin, Mikhail Agrachev, Henrik Eliasson, Tatiana Otroshchenko, Frank Krumeich, Rolf Erni, Evgenii V. Kondratenko and Javier Pérez-Ramírez
{"title":"在有缺陷的氮化硼上通过机械化学方法获得铁原子,以稳定生产丙烯","authors":"Gian Marco Beshara, Ivan Surin, Mikhail Agrachev, Henrik Eliasson, Tatiana Otroshchenko, Frank Krumeich, Rolf Erni, Evgenii V. Kondratenko and Javier Pérez-Ramírez","doi":"10.1039/D4EY00123K","DOIUrl":null,"url":null,"abstract":"<p >Single-atom catalysts (SACs), possessing a uniform metal site structure, are a promising class of materials for selective oxidations of hydrocarbons. However, their design for targeted applications requires careful choice of metal–host combinations and suitable synthetic techniques. Here, we report iron atoms stabilised on defective hexagonal boron nitride (h-BN) <em>via</em> mechanochemical activation in a ball mill as an effective catalyst for propylene production <em>via</em> N<small><sub>2</sub></small>O-mediated oxidative propane dehydrogenation (N<small><sub>2</sub></small>O-ODHP), reaching 95% selectivity at 6% propane conversion and maintaining stable performance for 40 h on stream. This solvent-free synthesis allows simultaneous carrier exfoliation and surface defect generation, creating anchoring sites for catalytically-active iron atoms. The incorporation of a small metal quantity (0.5 wt%) predominantly generates a mix of atomically-dispersed Fe<small><sup>2+</sup></small> and Fe<small><sup>3+</sup></small> species, as confirmed by combining advanced microscopy and electron paramagnetic resonance, UV-vis and X-ray photoelectron spectroscopy analyses. Single-atom iron favours selective propylene formation, while metal oxide nanoparticles yield large quantities of CO<small><sub><em>x</em></sub></small> and cracking by-products. The lack of acidic functionalities on h-BN, hindering coke formation, and firm stabilisation of Fe sites, preventing metal sintering, ensure stable operation. These findings showcase N<small><sub>2</sub></small>O-ODHP as a promising propylene production technology and foster wider adoption of mechanochemical activation as a viable method for SACs synthesis.</p>","PeriodicalId":72877,"journal":{"name":"EES catalysis","volume":" 6","pages":" 1263-1276"},"PeriodicalIF":0.0000,"publicationDate":"2024-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ey/d4ey00123k?page=search","citationCount":"0","resultStr":"{\"title\":\"Mechanochemically-derived iron atoms on defective boron nitride for stable propylene production†\",\"authors\":\"Gian Marco Beshara, Ivan Surin, Mikhail Agrachev, Henrik Eliasson, Tatiana Otroshchenko, Frank Krumeich, Rolf Erni, Evgenii V. Kondratenko and Javier Pérez-Ramírez\",\"doi\":\"10.1039/D4EY00123K\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Single-atom catalysts (SACs), possessing a uniform metal site structure, are a promising class of materials for selective oxidations of hydrocarbons. However, their design for targeted applications requires careful choice of metal–host combinations and suitable synthetic techniques. Here, we report iron atoms stabilised on defective hexagonal boron nitride (h-BN) <em>via</em> mechanochemical activation in a ball mill as an effective catalyst for propylene production <em>via</em> N<small><sub>2</sub></small>O-mediated oxidative propane dehydrogenation (N<small><sub>2</sub></small>O-ODHP), reaching 95% selectivity at 6% propane conversion and maintaining stable performance for 40 h on stream. This solvent-free synthesis allows simultaneous carrier exfoliation and surface defect generation, creating anchoring sites for catalytically-active iron atoms. The incorporation of a small metal quantity (0.5 wt%) predominantly generates a mix of atomically-dispersed Fe<small><sup>2+</sup></small> and Fe<small><sup>3+</sup></small> species, as confirmed by combining advanced microscopy and electron paramagnetic resonance, UV-vis and X-ray photoelectron spectroscopy analyses. Single-atom iron favours selective propylene formation, while metal oxide nanoparticles yield large quantities of CO<small><sub><em>x</em></sub></small> and cracking by-products. The lack of acidic functionalities on h-BN, hindering coke formation, and firm stabilisation of Fe sites, preventing metal sintering, ensure stable operation. These findings showcase N<small><sub>2</sub></small>O-ODHP as a promising propylene production technology and foster wider adoption of mechanochemical activation as a viable method for SACs synthesis.</p>\",\"PeriodicalId\":72877,\"journal\":{\"name\":\"EES catalysis\",\"volume\":\" 6\",\"pages\":\" 1263-1276\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2024-08-07\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.rsc.org/en/content/articlepdf/2024/ey/d4ey00123k?page=search\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"EES catalysis\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2024/ey/d4ey00123k\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"EES catalysis","FirstCategoryId":"1085","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/ey/d4ey00123k","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
Mechanochemically-derived iron atoms on defective boron nitride for stable propylene production†
Single-atom catalysts (SACs), possessing a uniform metal site structure, are a promising class of materials for selective oxidations of hydrocarbons. However, their design for targeted applications requires careful choice of metal–host combinations and suitable synthetic techniques. Here, we report iron atoms stabilised on defective hexagonal boron nitride (h-BN) via mechanochemical activation in a ball mill as an effective catalyst for propylene production via N2O-mediated oxidative propane dehydrogenation (N2O-ODHP), reaching 95% selectivity at 6% propane conversion and maintaining stable performance for 40 h on stream. This solvent-free synthesis allows simultaneous carrier exfoliation and surface defect generation, creating anchoring sites for catalytically-active iron atoms. The incorporation of a small metal quantity (0.5 wt%) predominantly generates a mix of atomically-dispersed Fe2+ and Fe3+ species, as confirmed by combining advanced microscopy and electron paramagnetic resonance, UV-vis and X-ray photoelectron spectroscopy analyses. Single-atom iron favours selective propylene formation, while metal oxide nanoparticles yield large quantities of COx and cracking by-products. The lack of acidic functionalities on h-BN, hindering coke formation, and firm stabilisation of Fe sites, preventing metal sintering, ensure stable operation. These findings showcase N2O-ODHP as a promising propylene production technology and foster wider adoption of mechanochemical activation as a viable method for SACs synthesis.