{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,6,5]],"date-time":"2026-06-05T07:23:09Z","timestamp":1780644189056,"version":"3.54.1"},"reference-count":57,"publisher":"Wiley","issue":"1","license":[{"start":{"date-parts":[[2022,11,24]],"date-time":"2022-11-24T00:00:00Z","timestamp":1669248000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["12204251"],"award-info":[{"award-number":["12204251"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["aces.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry \u0097 An Asian Journal"],"published-print":{"date-parts":[[2023,1,3]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The removal of impurity gases (N<jats:sub>2<\/jats:sub>, CO<jats:sub>2<\/jats:sub>) in natural gas is critical to the efficient use of natural gas. In this work, the selective adsorption for N<jats:sub>2<\/jats:sub> and CO<jats:sub>2<\/jats:sub> over CH<jats:sub>4<\/jats:sub> on MIL\u2010100\u2005(M) (M=<jats:sup>4<\/jats:sup>Cr, <jats:sup>10<\/jats:sup>Cr, <jats:sup>6<\/jats:sup>Fe, <jats:sup>1<\/jats:sup>In, <jats:sup>1<\/jats:sup>Sc, <jats:sup>3<\/jats:sup>V) is studied by density functional theory (DFT) calculations. The calculated adsorption energy of the large\u2010size cluster model (LC) of MIL\u2010100\u2005(M) shows that the <jats:sup>4<\/jats:sup>MIL\u2010100\u2005(<jats:sup>4<\/jats:sup>Cr) is the best at the refinement of natural gas due to the lower adsorption energy of CH<jats:sub>4<\/jats:sub> (\u22122.58\u2005kJ\/mol) in comparison with that of N<jats:sub>2<\/jats:sub> (\u221221.49\u2005kJ\/mol) and CO<jats:sub>2<\/jats:sub> (\u221223.82\u2005kJ\/mol). <jats:sup>1<\/jats:sup>MIL\u2010100\u2005(<jats:sup>1<\/jats:sup>Sc) and <jats:sup>1<\/jats:sup>MIL\u2010100\u2005(<jats:sup>6<\/jats:sup>Fe) can also achieve selective adsorption and follows the order <jats:sup>4<\/jats:sup>MIL\u2010100\u2005(<jats:sup>4<\/jats:sup>Cr)&gt;<jats:sup>1<\/jats:sup>MIL\u2010100\u2005(<jats:sup>1<\/jats:sup>Sc)&gt;<jats:sup>1<\/jats:sup>MIL\u2010100\u2005(<jats:sup>6<\/jats:sup>Fe). In the research of the selective adsorption mechanism of MIL\u2010100\u2005(M) (M=<jats:sup>4<\/jats:sup>Cr, <jats:sup>1<\/jats:sup>Sc, <jats:sup>6<\/jats:sup>Fe), the independent gradient model (IGM) indicates that these outstanding adsorbents interact with CO<jats:sub>2<\/jats:sub> and N<jats:sub>2<\/jats:sub> mainly through the electrostatic attractive interaction, while the van der Walls interaction dominates in the interaction with CH<jats:sub>4.<\/jats:sub> The atomic Projected Density of State (PDOS) further confirms that CH<jats:sub>4<\/jats:sub> contributes least to the intermolecular interaction than that of CO<jats:sub>2<\/jats:sub> and N<jats:sub>2<\/jats:sub>. Through the scrutiny of molecular orbitals, it is found that electrons transfer from the gas molecule to the metal site in the adsorption of CO<jats:sub>2<\/jats:sub> and N<jats:sub>2<\/jats:sub>. Not only does the type of the metallic orbitals, but also the delocalization of the involved orbitals determines the selective adsorption performance of MIL\u2010100. Both Cr and Sc share their <jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/asia202200985-math-0001.png\" xlink:title=\"urn:x-wiley:18614728:media:asia202200985:asia202200985-math-0001\"\/>\n orbitals with the gases, making <jats:sup>1<\/jats:sup>MIL\u2010100\u2005(<jats:sup>1<\/jats:sup>Sc) another potential effective separator for CH<jats:sub>4<\/jats:sub>. Additionally, the comparison of adsorption energy and PDOS shows that the introduction of ligands such as benzene impedes the electron donation from gas molecules (CO<jats:sub>2<\/jats:sub>, N<jats:sub>2<\/jats:sub>) to the metal site, indicating electron\u2010withdrawing ligands will further favor the adsorption.<\/jats:p>","DOI":"10.1002\/asia.202200985","type":"journal-article","created":{"date-parts":[[2022,11,3]],"date-time":"2022-11-03T09:44:52Z","timestamp":1667468692000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":7,"title":["Theoretical Investigations on MIL\u2010100(M) (M=Cr, Sc, Fe) with High Adsorption Selectivity for Nitrogen and Carbon Dioxide over Methane"],"prefix":"10.1002","volume":"18","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-9767-089X","authenticated-orcid":false,"given":"Fan","family":"Huang","sequence":"first","affiliation":[{"name":"Institute of Modern Optics Tianjin Key Laboratory of Micro-scale Optical Information Science and Technology Nankai University  Tianjin 300350 P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xu","family":"Zhang","sequence":"additional","affiliation":[{"name":"Institute of Modern Optics Tianjin Key Laboratory of Micro-scale Optical Information Science and Technology Nankai University  Tianjin 300350 P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Weiwei","family":"Liu","sequence":"additional","affiliation":[{"name":"Institute of Modern Optics Tianjin Key Laboratory of Micro-scale Optical Information Science and Technology Nankai University  Tianjin 300350 P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Junkuo","family":"Gao","sequence":"additional","affiliation":[{"name":"Institute of Functional Porous Materials The Key laboratory of Advanced Textile Materials and Manufacturing Technology of Ministry of Education School of Materials Science and Engineering Zhejiang Sci-Tech University  Hangzhou 310018 P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0731-2317","authenticated-orcid":false,"given":"Lu","family":"Sun","sequence":"additional","affiliation":[{"name":"Institute of Modern Optics Tianjin Key Laboratory of Micro-scale Optical Information Science and Technology Nankai University  Tianjin 300350 P. R. 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