Gerson J. Leonel, Mohit Verma, Godwin A. Agbanga, Laura Bonatti, Hakim Boukhalfa, Alexandra Navrotsky, Hongwu Xu
{"title":"基于1,3,5-苯三羧酸酯连接剂和稀土金属的金属有机骨架的热力学稳定性","authors":"Gerson J. Leonel, Mohit Verma, Godwin A. Agbanga, Laura Bonatti, Hakim Boukhalfa, Alexandra Navrotsky, Hongwu Xu","doi":"10.1007/s00269-024-01303-7","DOIUrl":null,"url":null,"abstract":"<div><p>This work systematically investigates the thermodynamic stability in M-BTC metal organic frameworks, where M = Y, Eu, or La and BTC = (1,3,5-benzenetricarboxylate) linker. Enthalpies of formation obtained from calorimetric measurements of Y(BTC)·5.43(H<sub>2</sub>O), Eu(BTC)·5.82(H<sub>2</sub>O) and La(BTC)·4.85(H<sub>2</sub>O) enable determination of the energetic landscape for metal substitution (Y, Eu, and La) in M-BTC materials. The enthalpies of formation from linker plus metal of La-BTC, Eu-BTC, and Y-BTC are − 3219.3 ± 3.4, 3.9 ± 2.0 and 713.3 ± 3.0 kJ mol<sup>− 1</sup><sub>,</sub> respectively. The highly endothermic enthalpy of formation of Y(BTC)·5.43(H<sub>2</sub>O) reflects a thermodynamic penalty for a change in the coordination environment of Y metal atoms in the BTC framework compared to Y<sub>2</sub>O<sub>3</sub>. The high thermodynamic stability of the M-BTC framework employing La metal confirms greater stabilization from the use of larger metal atoms in frameworks with oxygen-based linkers. The results from thermodynamic analysis suggest water is a stabilizing agent. Thus, the choice of metal atom and presence of guest water molecules can enthalpically stabilize the M-BTC materials by as much as ~ 3932 kJ mol<sup>− 1</sup>. More broadly, the results indicate complex interplay among choice of metal, water content, and thermodynamic stability in M-BTC frameworks.</p></div>","PeriodicalId":20132,"journal":{"name":"Physics and Chemistry of Minerals","volume":"52 2","pages":""},"PeriodicalIF":1.2000,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Thermodynamic stabilization in metal organic frameworks based on 1,3,5-benzenetricarboxylate linkers and rare earth metals\",\"authors\":\"Gerson J. Leonel, Mohit Verma, Godwin A. Agbanga, Laura Bonatti, Hakim Boukhalfa, Alexandra Navrotsky, Hongwu Xu\",\"doi\":\"10.1007/s00269-024-01303-7\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>This work systematically investigates the thermodynamic stability in M-BTC metal organic frameworks, where M = Y, Eu, or La and BTC = (1,3,5-benzenetricarboxylate) linker. Enthalpies of formation obtained from calorimetric measurements of Y(BTC)·5.43(H<sub>2</sub>O), Eu(BTC)·5.82(H<sub>2</sub>O) and La(BTC)·4.85(H<sub>2</sub>O) enable determination of the energetic landscape for metal substitution (Y, Eu, and La) in M-BTC materials. The enthalpies of formation from linker plus metal of La-BTC, Eu-BTC, and Y-BTC are − 3219.3 ± 3.4, 3.9 ± 2.0 and 713.3 ± 3.0 kJ mol<sup>− 1</sup><sub>,</sub> respectively. The highly endothermic enthalpy of formation of Y(BTC)·5.43(H<sub>2</sub>O) reflects a thermodynamic penalty for a change in the coordination environment of Y metal atoms in the BTC framework compared to Y<sub>2</sub>O<sub>3</sub>. The high thermodynamic stability of the M-BTC framework employing La metal confirms greater stabilization from the use of larger metal atoms in frameworks with oxygen-based linkers. The results from thermodynamic analysis suggest water is a stabilizing agent. Thus, the choice of metal atom and presence of guest water molecules can enthalpically stabilize the M-BTC materials by as much as ~ 3932 kJ mol<sup>− 1</sup>. More broadly, the results indicate complex interplay among choice of metal, water content, and thermodynamic stability in M-BTC frameworks.</p></div>\",\"PeriodicalId\":20132,\"journal\":{\"name\":\"Physics and Chemistry of Minerals\",\"volume\":\"52 2\",\"pages\":\"\"},\"PeriodicalIF\":1.2000,\"publicationDate\":\"2025-03-05\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Physics and Chemistry of Minerals\",\"FirstCategoryId\":\"89\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s00269-024-01303-7\",\"RegionNum\":4,\"RegionCategory\":\"地球科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"MATERIALS SCIENCE, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Physics and Chemistry of Minerals","FirstCategoryId":"89","ListUrlMain":"https://link.springer.com/article/10.1007/s00269-024-01303-7","RegionNum":4,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
Thermodynamic stabilization in metal organic frameworks based on 1,3,5-benzenetricarboxylate linkers and rare earth metals
This work systematically investigates the thermodynamic stability in M-BTC metal organic frameworks, where M = Y, Eu, or La and BTC = (1,3,5-benzenetricarboxylate) linker. Enthalpies of formation obtained from calorimetric measurements of Y(BTC)·5.43(H2O), Eu(BTC)·5.82(H2O) and La(BTC)·4.85(H2O) enable determination of the energetic landscape for metal substitution (Y, Eu, and La) in M-BTC materials. The enthalpies of formation from linker plus metal of La-BTC, Eu-BTC, and Y-BTC are − 3219.3 ± 3.4, 3.9 ± 2.0 and 713.3 ± 3.0 kJ mol− 1, respectively. The highly endothermic enthalpy of formation of Y(BTC)·5.43(H2O) reflects a thermodynamic penalty for a change in the coordination environment of Y metal atoms in the BTC framework compared to Y2O3. The high thermodynamic stability of the M-BTC framework employing La metal confirms greater stabilization from the use of larger metal atoms in frameworks with oxygen-based linkers. The results from thermodynamic analysis suggest water is a stabilizing agent. Thus, the choice of metal atom and presence of guest water molecules can enthalpically stabilize the M-BTC materials by as much as ~ 3932 kJ mol− 1. More broadly, the results indicate complex interplay among choice of metal, water content, and thermodynamic stability in M-BTC frameworks.
期刊介绍：
Physics and Chemistry of Minerals is an international journal devoted to publishing articles and short communications of physical or chemical studies on minerals or solids related to minerals. The aim of the journal is to support competent interdisciplinary work in mineralogy and physics or chemistry. Particular emphasis is placed on applications of modern techniques or new theories and models to interpret atomic structures and physical or chemical properties of minerals. Some subjects of interest are:
-Relationships between atomic structure and crystalline state (structures of various states, crystal energies, crystal growth, thermodynamic studies, phase transformations, solid solution, exsolution phenomena, etc.)
-General solid state spectroscopy (ultraviolet, visible, infrared, Raman, ESCA, luminescence, X-ray, electron paramagnetic resonance, nuclear magnetic resonance, gamma ray resonance, etc.)
-Experimental and theoretical analysis of chemical bonding in minerals (application of crystal field, molecular orbital, band theories, etc.)
-Physical properties (magnetic, mechanical, electric, optical, thermodynamic, etc.)
-Relations between thermal expansion, compressibility, elastic constants, and fundamental properties of atomic structure, particularly as applied to geophysical problems
-Electron microscopy in support of physical and chemical studies
-Computational methods in the study of the structure and properties of minerals
-Mineral surfaces (experimental methods, structure and properties)
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