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

Carolina Carrillo-Carrión, Judit Farrando-Perez, Luke L. Daemen, Yongqiang Q. Cheng, Anibal J. Ramirez-Cuesta, Joaquin Silvestre-Albero

Research output: Contribution to journalArticlepeer-review

5 Scopus citations

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.

Original languageEnglish
Article numbere202315280
JournalAngewandte Chemie - International Edition
Volume63
Issue number6
DOIs
StatePublished - Feb 5 2024
Externally publishedYes

Funding

Authors would like to acknowledge financial support from Ministerio de Ciencia e Innovación (Project PID2019‐108453GB‐C21 and PID2022‐141034OB‐C22), Consejo Superior de Investigaciones Científicas (CSIC) for internal funds (Intramural project, 202280I170), and Conselleria de Innovación, Universidades, Ciencia y Sociedad Digital (Project CIPROM/2021/022). A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory (project IPTS‐29742.1). Authors would like to acknowledge financial support from Ministerio de Ciencia e Innovación (Project PID2019-108453GB-C21 and PID2022-141034OB-C22), Consejo Superior de Investigaciones Científicas (CSIC) for internal funds (Intramural project, 202280I170), and Conselleria de Innovación, Universidades, Ciencia y Sociedad Digital (Project CIPROM/2021/022). A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory (project IPTS-29742.1).

Keywords

  • Confinement Effects
  • Gas Hydrates
  • Hydrogen Storage
  • Metal–Organic Frameworks
  • Zirconium-Metalloporphyrin Framework

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