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<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&#xa0;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&#xa0;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>

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Thermodynamic stabilization in metal organic frameworks based on 1,3,5-benzenetricarboxylate linkers and rare earth metals

  • 期刊论文

  • 发表日期：

    2025年3月5日

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  • Gerson J. Leonel,
  • Mohit Verma,
  • Godwin A. Agbanga,
  • Laura Bonatti,
  • Hakim Boukhalfa,
  • Alexandra Navrotsky,
  • Hongwu Xu

摘要

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.