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

• Published in: Angewandte Chemie Vol. 136; no. 6
• Main Authors: Carrillo‐Carrión, Carolina, Farrando‐Perez, Judit, Daemen, Luke L., Cheng, Yongqiang Q., Ramirez‐Cuesta, Anibal J., Silvestre‐Albero, Joaquin
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 05.02.2024
• Subjects: Clathrates; Confinement Effects; Energy conservation; Gas Hydrates; Homogeneity; Hydrogen; Hydrogen Storage; Metal-organic frameworks; Nucleation; Open channels; Porphyrins; Zirconium; Zirconium-Metalloporphyrin Framework
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.202315280

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. Microwave‐assisted PCN‐222 nanocrystals has been successfully used as nanoreactors to promote the nucleation and growth of hydrogen clathrates. This research shows that hydrogen can be enclathrated at lower pressure than the bulk system, with fast kinetics and with a nearly complete water‐to‐hydrate conversion.