# Transformation of a Metal-organic Framework for Tuned Catalytic Activity

## TL;DR

This paper explores how modifying UiO-66(Zr) MOFs through functionalization and defect creation enhances their catalytic activity for converting benzene alcohol to benzedehyate, combining computational and experimental insights.

## Contribution

It introduces two novel strategies—ligand functionalization and defect engineering—to tune MOF electronic structures for improved catalysis.

## Key findings

- Functional groups reduce the optical band gap by 1 eV.
- Defects shift the HOMO energy, affecting catalytic properties.
- Combined approaches enhance catalytic conversion and selectivity.

## Abstract

Metal-organic frameworks (MOFs) are an attractive substrate for catalytic reactions due to the high area density of reaction sites and the ability to tailor an array of material attributes. This study focuses on a thermally stable crystalline UiO-66(Zr) MOF structure and the modulation of the electronic structure using two strategies to improve the catalytic conversion and selectivity of benzene alcohol to benzedehyate. Those two strategies include the functionalization of the organic struts with branched ligands and manually creating structural defects with unsaturated organic linkers. A combination of computational and experimental results provide evidence of improved catalytic activity of MOFs via these two approaches. Functional groups attached to the main organic strut modify the electronic environment of the photoactive aromatic carbon and thereby decrease the optical band gap by 1eV. Whereas the introduction of structural defects due to the organic linker desaturation provided a shift in the HUMO as a result of the decrease in strut coordination with the inorganic knots.