Spatial distribution modulation of mixed building blocks in metal-organic frameworks

Area of Science:

• Materials Science
• Chemistry
• Nanotechnology

Background:

• Precise placement of mixed building blocks in metal-organic frameworks (MOFs) is crucial for designing specific pore environments.
• Tailoring MOF microstructures is key for advanced applications in catalysis, separation, and sensing.

Purpose of the Study:

• To demonstrate a method for controlling the spatial distribution of building blocks within MOFs.
• To achieve controlled microstructures (core-shell, uniform) in MOFs through temperature modulation.

Main Methods:

• Exploiting differential temperature sensitivities of diffusion coefficients and exchange rates of MOF building blocks.
• Tuning reaction temperature during forward linker exchange between isoreticular MOFs.
• Applying post-synthetic metal exchange for modulating framework metal ion distribution.

Main Results:

• Achieved control over spatial distribution of mixed building blocks in MOFs by temperature tuning.
• Fabricated core-shell and uniform microstructural MOFs via controlled linker exchange.
• Extended the strategy to create inverted core-shell and multi-shell MOF structures.
• Successfully modulated metal ion distribution in Zn-based MOFs to Ni-based MOFs.

Conclusions:

• Temperature-controlled linker exchange is an effective strategy for precise MOF microstructure engineering.
• This approach allows for the rational design of complex MOF architectures with tailored properties.
• The methodology is versatile, applicable to both linker and metal site modifications in MOFs.