Zr‐Porphyrin Metal–Organic Framework as nanoreactor for boosting the formation of hydrogen clathrates

Journal Article · 29 December 2023 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202315280 · OSTI ID:2267589

Carrillo‐Carrión, Carolina ^[1]; Farrando‐Perez, Judit ^[2]; Daemen, Luke L. ^[3]; Cheng, Yongqiang Q. ^[3]; Ramirez‐Cuesta, Anibal J. ^[3]; Silvestre‐Albero, Joaquin  ^[2]

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1. Institute for Chemical Research (IIQ) CSIC – University of Seville 41092 Seville Spain
2. Laboratorio de Materiales Avanzados Departamento de Química Inorgánica-Instituto Universitario de Materiales Universidad de Alicante 03690 San Vicente del Raspeig Spain
3. Spallation Neutron Source Oak Ridge National Laboratory Oak Ridge TN 37831 USA

Abstract We report the first experimental evidence for rapid formation of hydrogen clathrates under mild pressure and temperature conditions within the cavities of a zirconium‐metalloporphyrin framework, specifically PCN‐222. PCN‐222 has been selected for its 1D mesoporous channels, high water‐stability, and proper hydrophilic behavior. Firstly, we optimize a microwave (MW)‐assisted method for the synthesis of nanosized PCN‐222 particles with precise structure control (exceptional homogeneity in morphology and crystalline phase purity), taking advantage of MW in terms of rapid/homogeneous heating, time and energy savings, as well as potential scalability of the synthetic method. Second, we explore the relevance of the large mesoporous 1D open channels within the PCN‐222 to promote the nucleation and growth of confined hydrogen clathrates. Experimental results show that PCN‐222 drives the nucleation process at a lower pressure than the bulk system (1.35 kbar vs 2 kbar), with fast kinetics (minutes), using pure water, and with a nearly complete water‐to‐hydrate conversion. Unfortunately, PCN‐222 cannot withstand these high pressures, which lead to a significant alteration of the mesoporous structure while the microporous network remains mainly unchanged.

• Sponsoring Organization: USDOE
• OSTI ID: 2267589
• Alternate ID(s): OSTI ID: 2267590
• Journal Information: Angewandte Chemie, Journal Name: Angewandte Chemie Vol. 136 Journal Issue: 6; ISSN 0044-8249
• Publisher: Wiley Blackwell (John Wiley & Sons)Copyright Statement
• Country of Publication: Germany
• Language: English