In theory, bimetallic UiO-66(Zr:Ce) and UiO-66(Zr:Hf) metal-organic frameworks (MOFs) are extremely versatile and attractive nanoporous materials as they combine the high catalytic activity of UiO-66(Ce) or UiO-66(Hf) with the outstanding stability of UiO-66(Zr). Using in situ high-pressure powder X-ray diffraction, however, we observe that this expected mechanical stability is not achieved when incorporating cerium or hafnium in UiO-66(Zr). This observation is akin to the earlier observed reduced thermal stability of UiO-66(Zr:Ce) compounds. To elucidate the atomic origin of this phenomenon, we chart the loss-of-crystallinity pressures of 22 monometallic and bimetallic UiO-66 materials and systematically isolate their intrinsic mechanical stability from their defect-induced weakening. This complementary experimental/computational approach reveals that the intrinsic mechanical stability of these bimetallic MOFs decreases nonlinearly upon cerium incorporation but remains unaffected by the zirconium: hafnium ratio. Additionally, all experimental samples suffer from defect-induced weakening, a synthesis-controlled effect that is observed to be independent of their intrinsic stability.

Charting the Metal-Dependent High-Pressure Stability of Bimetallic UiO-66 Materials / Rogge, S. M. J.; Yot, P. G.; Jacobsen, J.; Muniz Miranda, F.; Vandenbrande, S.; Gosch, J.; Ortiz, V.; Collings, I. E.; Devautour-Vinot, S.; Maurin, G.; Stock, N.; Van Speybroeck, V.. - In: ACS MATERIALS LETTERS. - ISSN 2639-4979. - 2:4(2020), pp. 438-445. [10.1021/acsmaterialslett.0c00042]

Charting the Metal-Dependent High-Pressure Stability of Bimetallic UiO-66 Materials

Muniz Miranda F.;
2020-01-01

Abstract

In theory, bimetallic UiO-66(Zr:Ce) and UiO-66(Zr:Hf) metal-organic frameworks (MOFs) are extremely versatile and attractive nanoporous materials as they combine the high catalytic activity of UiO-66(Ce) or UiO-66(Hf) with the outstanding stability of UiO-66(Zr). Using in situ high-pressure powder X-ray diffraction, however, we observe that this expected mechanical stability is not achieved when incorporating cerium or hafnium in UiO-66(Zr). This observation is akin to the earlier observed reduced thermal stability of UiO-66(Zr:Ce) compounds. To elucidate the atomic origin of this phenomenon, we chart the loss-of-crystallinity pressures of 22 monometallic and bimetallic UiO-66 materials and systematically isolate their intrinsic mechanical stability from their defect-induced weakening. This complementary experimental/computational approach reveals that the intrinsic mechanical stability of these bimetallic MOFs decreases nonlinearly upon cerium incorporation but remains unaffected by the zirconium: hafnium ratio. Additionally, all experimental samples suffer from defect-induced weakening, a synthesis-controlled effect that is observed to be independent of their intrinsic stability.
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Charting the Metal-Dependent High-Pressure Stability of Bimetallic UiO-66 Materials / Rogge, S. M. J.; Yot, P. G.; Jacobsen, J.; Muniz Miranda, F.; Vandenbrande, S.; Gosch, J.; Ortiz, V.; Collings, I. E.; Devautour-Vinot, S.; Maurin, G.; Stock, N.; Van Speybroeck, V.. - In: ACS MATERIALS LETTERS. - ISSN 2639-4979. - 2:4(2020), pp. 438-445. [10.1021/acsmaterialslett.0c00042]
Rogge, S. M. J.; Yot, P. G.; Jacobsen, J.; Muniz Miranda, F.; Vandenbrande, S.; Gosch, J.; Ortiz, V.; Collings, I. E.; Devautour-Vinot, S.; Maurin, G.; Stock, N.; Van Speybroeck, V.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11380/1258617
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