Qiming Tang, Xueling Lei, Yongliang Zhang, Jiaxin Lu, Kevin Huang
{"title":"了解贵金属在氢还原氧化铁过程中的催化作用:DFT 计算的启示","authors":"Qiming Tang, Xueling Lei, Yongliang Zhang, Jiaxin Lu, Kevin Huang","doi":"10.1039/d4ta04793a","DOIUrl":null,"url":null,"abstract":"Fe/FeOx redox couples have been widely used as an oxygen carrier for redox devices such as chemical looping reactors and solid oxide iron-air battery (SOIAB) because of their low cost and high oxygen capacity. However, a critical challenge is the sluggish reduction kinetics of FeOx in the intermediate temperature range, significantly limiting the devices’ achievable efficiency and service life. Here, we report on a combined theoretical and experimental study on the catalytic effect of noble metals (Ir, Ru, Rh, Pd and Pt) on the H2-reduction kinetics of FeOx. We first use density functional theory (DFT) to calculate the electron projected density of states (PDOS) near Fermi level (EF) of several noble metal (Ir, Pd, Ru, Rh, Pd)/Fe3O4 systems. We reveal that Ir offers the highest PDOS near EF among all noble metals studied, which provides abundant electrons for efficient cleavage of O-Fe bonds and low-energy dissociation of H2 molecules, thus resulting in significantly boosted reduction kinetics of Fe3O4. Experimentally, the results of temperature programmed reduction and SOIAB performance testing corroborate the theoretical predictions.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":10.7000,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Understanding the Catalysis of Noble Metals in Reduction of Iron Oxide by Hydrogen: Insights from DFT Calculations\",\"authors\":\"Qiming Tang, Xueling Lei, Yongliang Zhang, Jiaxin Lu, Kevin Huang\",\"doi\":\"10.1039/d4ta04793a\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Fe/FeOx redox couples have been widely used as an oxygen carrier for redox devices such as chemical looping reactors and solid oxide iron-air battery (SOIAB) because of their low cost and high oxygen capacity. However, a critical challenge is the sluggish reduction kinetics of FeOx in the intermediate temperature range, significantly limiting the devices’ achievable efficiency and service life. Here, we report on a combined theoretical and experimental study on the catalytic effect of noble metals (Ir, Ru, Rh, Pd and Pt) on the H2-reduction kinetics of FeOx. We first use density functional theory (DFT) to calculate the electron projected density of states (PDOS) near Fermi level (EF) of several noble metal (Ir, Pd, Ru, Rh, Pd)/Fe3O4 systems. We reveal that Ir offers the highest PDOS near EF among all noble metals studied, which provides abundant electrons for efficient cleavage of O-Fe bonds and low-energy dissociation of H2 molecules, thus resulting in significantly boosted reduction kinetics of Fe3O4. Experimentally, the results of temperature programmed reduction and SOIAB performance testing corroborate the theoretical predictions.\",\"PeriodicalId\":82,\"journal\":{\"name\":\"Journal of Materials Chemistry A\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":10.7000,\"publicationDate\":\"2024-10-18\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Materials Chemistry A\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://doi.org/10.1039/d4ta04793a\",\"RegionNum\":2,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Materials Chemistry A","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1039/d4ta04793a","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Understanding the Catalysis of Noble Metals in Reduction of Iron Oxide by Hydrogen: Insights from DFT Calculations
Fe/FeOx redox couples have been widely used as an oxygen carrier for redox devices such as chemical looping reactors and solid oxide iron-air battery (SOIAB) because of their low cost and high oxygen capacity. However, a critical challenge is the sluggish reduction kinetics of FeOx in the intermediate temperature range, significantly limiting the devices’ achievable efficiency and service life. Here, we report on a combined theoretical and experimental study on the catalytic effect of noble metals (Ir, Ru, Rh, Pd and Pt) on the H2-reduction kinetics of FeOx. We first use density functional theory (DFT) to calculate the electron projected density of states (PDOS) near Fermi level (EF) of several noble metal (Ir, Pd, Ru, Rh, Pd)/Fe3O4 systems. We reveal that Ir offers the highest PDOS near EF among all noble metals studied, which provides abundant electrons for efficient cleavage of O-Fe bonds and low-energy dissociation of H2 molecules, thus resulting in significantly boosted reduction kinetics of Fe3O4. Experimentally, the results of temperature programmed reduction and SOIAB performance testing corroborate the theoretical predictions.
期刊介绍:
The Journal of Materials Chemistry A, B & C covers a wide range of high-quality studies in the field of materials chemistry, with each section focusing on specific applications of the materials studied. Journal of Materials Chemistry A emphasizes applications in energy and sustainability, including topics such as artificial photosynthesis, batteries, and fuel cells. Journal of Materials Chemistry B focuses on applications in biology and medicine, while Journal of Materials Chemistry C covers applications in optical, magnetic, and electronic devices. Example topic areas within the scope of Journal of Materials Chemistry A include catalysis, green/sustainable materials, sensors, and water treatment, among others.