Lewis basicity generated by localised charge imbalance in noble metal nanoparticle-embedded defective metal-organic...

Interactions between metal nanoparticles (NPs) and metal-organic frameworks (MOFs) in their composite forms have proven to exhibit beneficial properties, such as enhanced catalytic performance through synergistic effects. Herein, we show that Lewis basic sites can be created within an anionic defective MOF by engineering the electronic state of the pendant carboxylate groups situated at the defect sites. This is achieved from the concerted interactions between the pendant carboxylate groups, embedded Pd NPs and charge-balancing cations (Mⁿ⁺ = Ce³⁺, Co²⁺, Ni²⁺, Cu²⁺, Mg²⁺, Li⁺, Na⁺ or K⁺). This work is the first example of generating a new collective property, i.e. Lewis basicity, in metal-carboxylate MOFs. Importantly, the choice of Mⁿ⁺, used during cation exchange, acts as a convenient parameter to tune the Lewis basicity of the MOF-based nanocomposites. It also provides a facile way to incorporate active metal sites and basic sites within carboxylate-based MOFs to engineer multifunctional nanocatalysts.