Fei Xie , Chengcheng Yuan , Haiyan Tan , Alireza Z. Moshfegh , Bicheng Zhu , Jiaguo Yu
{"title":"d波段中心调控过渡金属单原子负载COF对O2的吸附：DFT研究","authors":"Fei Xie , Chengcheng Yuan , Haiyan Tan , Alireza Z. Moshfegh , Bicheng Zhu , Jiaguo Yu","doi":"10.3866/PKU.WHXB202407013","DOIUrl":null,"url":null,"abstract":"<div><div>Covalent organic framework (COF) materials are promising photocatalysts because of their fantastic structural and physicochemical features. To enhance photocatalytic performance, numerous metal single atoms (MSA) are loaded on COF to improve molecule adsorption. However, the inherent mechanisms and dominant factors of the heightened adsorption property are not deeply unveiled. Herein, four MSA-COF systems were constructed by severally introducing Fe, Co, Ni, and Cu single atoms in monolayer TpBpy-COF. The effect of various metal atoms modification on the electronic property and O<sub>2</sub> adsorption of COF was investigated using density functional theory calculations. The results show that the metal atoms are bonded to the pyridinic N atoms, forming stable MSA-COF configurations. The anchoring of metal atoms reduces the band gap and raises the Fermi level of COF. Moreover, as the atomic number of the metals increases, the <em>d</em> orbitals of the metal atoms gradually move to lower energy levels, manifesting a negative shift of the <em>d</em>-band centers. After metal atoms loading, the weak physical adsorption of O<sub>2</sub> on pristine COF is converted to robust chemisorption with the formation of M―O<sub>ads</sub> bonds and intense electron transfer. Intriguingly, the adsorption energy presents a strong correlation with the <em>d</em>-band centers of the metal atoms. This finding is comprehended from the perspective of electron occupancy in antibonding orbitals in the adsorption systems. This work provides a feasible approach for modifying molecule adsorption on MSA-COF by regulating the <em>d</em>-band centers of metal atoms.</div><div><span><figure><span><img><ol><li><span><span>Download: <span>Download high-res image (95KB)</span></span></span></li><li><span><span>Download: <span>Download full-size image</span></span></span></li></ol></span></figure></span></div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"40 11","pages":"Article 2407013"},"PeriodicalIF":10.8000,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"d-Band Center Regulated O2 Adsorption on Transition Metal Single Atoms Loaded COF: A DFT Study\",\"authors\":\"Fei Xie , Chengcheng Yuan , Haiyan Tan , Alireza Z. Moshfegh , Bicheng Zhu , Jiaguo Yu\",\"doi\":\"10.3866/PKU.WHXB202407013\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Covalent organic framework (COF) materials are promising photocatalysts because of their fantastic structural and physicochemical features. To enhance photocatalytic performance, numerous metal single atoms (MSA) are loaded on COF to improve molecule adsorption. However, the inherent mechanisms and dominant factors of the heightened adsorption property are not deeply unveiled. Herein, four MSA-COF systems were constructed by severally introducing Fe, Co, Ni, and Cu single atoms in monolayer TpBpy-COF. The effect of various metal atoms modification on the electronic property and O<sub>2</sub> adsorption of COF was investigated using density functional theory calculations. The results show that the metal atoms are bonded to the pyridinic N atoms, forming stable MSA-COF configurations. The anchoring of metal atoms reduces the band gap and raises the Fermi level of COF. Moreover, as the atomic number of the metals increases, the <em>d</em> orbitals of the metal atoms gradually move to lower energy levels, manifesting a negative shift of the <em>d</em>-band centers. After metal atoms loading, the weak physical adsorption of O<sub>2</sub> on pristine COF is converted to robust chemisorption with the formation of M―O<sub>ads</sub> bonds and intense electron transfer. Intriguingly, the adsorption energy presents a strong correlation with the <em>d</em>-band centers of the metal atoms. This finding is comprehended from the perspective of electron occupancy in antibonding orbitals in the adsorption systems. This work provides a feasible approach for modifying molecule adsorption on MSA-COF by regulating the <em>d</em>-band centers of metal atoms.</div><div><span><figure><span><img><ol><li><span><span>Download: <span>Download high-res image (95KB)</span></span></span></li><li><span><span>Download: <span>Download full-size image</span></span></span></li></ol></span></figure></span></div></div>\",\"PeriodicalId\":6964,\"journal\":{\"name\":\"物理化学学报\",\"volume\":\"40 11\",\"pages\":\"Article 2407013\"},\"PeriodicalIF\":10.8000,\"publicationDate\":\"2024-11-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"物理化学学报\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S1000681824001747\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"物理化学学报","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1000681824001747","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
d-Band Center Regulated O2 Adsorption on Transition Metal Single Atoms Loaded COF: A DFT Study
Covalent organic framework (COF) materials are promising photocatalysts because of their fantastic structural and physicochemical features. To enhance photocatalytic performance, numerous metal single atoms (MSA) are loaded on COF to improve molecule adsorption. However, the inherent mechanisms and dominant factors of the heightened adsorption property are not deeply unveiled. Herein, four MSA-COF systems were constructed by severally introducing Fe, Co, Ni, and Cu single atoms in monolayer TpBpy-COF. The effect of various metal atoms modification on the electronic property and O2 adsorption of COF was investigated using density functional theory calculations. The results show that the metal atoms are bonded to the pyridinic N atoms, forming stable MSA-COF configurations. The anchoring of metal atoms reduces the band gap and raises the Fermi level of COF. Moreover, as the atomic number of the metals increases, the d orbitals of the metal atoms gradually move to lower energy levels, manifesting a negative shift of the d-band centers. After metal atoms loading, the weak physical adsorption of O2 on pristine COF is converted to robust chemisorption with the formation of M―Oads bonds and intense electron transfer. Intriguingly, the adsorption energy presents a strong correlation with the d-band centers of the metal atoms. This finding is comprehended from the perspective of electron occupancy in antibonding orbitals in the adsorption systems. This work provides a feasible approach for modifying molecule adsorption on MSA-COF by regulating the d-band centers of metal atoms.
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