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Water sorption studies with mesoporous multivariate monoliths based on UiO-66.

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Summary

Hierarchical linker thermolysis enhances porosity in monolithic metal-organic frameworks (MOFs). This method increases gas uptake and pore size, demonstrating potential for improved material performance.

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Area of Science:

  • Materials Science
  • Chemistry
  • Nanotechnology

Background:

  • Metal-organic frameworks (MOFs) offer tunable porosity for various applications.
  • Enhancing pore size and surface area in monolithic MOFs is crucial for performance.
  • Hierarchical linker thermolysis is a known method for powder MOFs.

Purpose of the Study:

  • To apply hierarchical linker thermolysis to monolithic MOFs for the first time.
  • To investigate the effect of thermolabile linker decomposition on MOF porosity.
  • To evaluate the water sorption performance of the modified monolithic MOFs.

Main Methods:

  • Synthesis of monolithic UiO-66-based MOFs with mixed linkers, including 2-aminoterephthalic acid (BDC-NH2).
  • Thermolysis of the BDC-NH2 linker at approximately 350 °C to induce mesopore formation.
  • Nitrogen and water sorption analysis to quantify changes in porosity and uptake capacity.

Main Results:

  • Thermolysis successfully created mesopores in the monolithic MOFs.
  • Gas uptake increased by over 200 cm³ g⁻¹, with enhanced pore volume and mean pore width.
  • The modified MOF exhibited a maximum water vapor uptake of 61.0 wt%, outperforming parent materials, while a highly mesoporous version showed lower uptake (36.2 wt%).

Conclusions:

  • Hierarchical linker thermolysis is effective in enhancing porosity of monolithic MOFs.
  • The presence of hydrophilic functional groups, like -NH2, is vital for high water uptake.
  • This study extends a known technique to a new material format, demonstrating its potential for tailored MOF properties.