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Bandgap Modulation in Zr-Based Metal-Organic Frameworks by Mixed-Linker Approach.
Rushie Mae Cedeno1,2, Ruel Cedeno3,2, Maebienne Anjelica Gapol2
1Department of Chemistry, University of Science and Technology of Southern Philippines, Claro M. Recto Avenue, Cagayan de Oro City 9000, Philippines.
Inorganic Chemistry
|June 10, 2021
Summary
Mixed organic linkers in metal-organic frameworks (MOFs) create mid-gap states, reducing bandgaps unexpectedly. This effect, influenced by linker interactions like π-π stacking, offers a new way to tune MOF electronic properties.
Area of Science:
- Materials Science
- Computational Chemistry
- Solid-State Physics
Background:
- Metal-organic frameworks (MOFs) offer tunable electronic properties via linker functionalization for diverse applications.
- Zirconium-based MOFs like UiO-66 and MIL-140A are promising for optoelectronics and sensing.
- Understanding bandgap modulation is crucial for designing MOFs with specific electronic functionalities.
Purpose of the Study:
- Investigate the impact of mixed organic linkers on the bandgap of UiO-66 and MIL-140A MOFs.
- Determine the underlying mechanisms responsible for bandgap changes in mixed-linker systems.
- Explore the role of structural features, specifically π-π stacking, in bandgap modulation.
Main Methods:
- Density Functional Theory (DFT) calculations were employed to simulate MOF structures and electronic properties.
- Total and partial density of states (DOS) were computed to analyze electronic band structures.
- Comparative analysis of single-linker and mixed-linker MOF systems was performed.
Main Results:
- Mixed-linker MOFs exhibited bandgaps that deviated from Vegard's law, forming mid-gap states.
- Bandgap reduction was observed in mixed-linker systems due to these mid-gap states.
- The bandgap modulation effect was more pronounced in MIL-140A than UiO-66, attributed to π-π stacking interactions.
Conclusions:
- Mixed-linker strategies can effectively engineer MOF electronic properties, deviating from simple intermediate bandgaps.
- The presence and strength of π-π stacking interactions significantly influence bandgap reduction.
- Distinct structural features, such as linker orientation and stacking, are critical for controlling MOF bandgaps.
