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Selective Inclusion of Extra-Framework Ligands in Nanoporous Vanadium-Based Frameworks Using an Optimized Synthesis Approach for Potential Applications in Catalysis and Separation
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DOI：10.1021/acsanm.6c01368.png)
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Abstract
En 中文
Metal–organic frameworks (MOFs) are nanoporous, crystalline materials with highly tunable structures. Here, we investigate the concept of extra-framework ligands as a strategy for accessing additional tunability in MOFs. Specifically, we used a combination of initial synthetic exploration and subsequent Latin hypercube sampling (LHS) and Bayesian optimization campaigns to synthetically incorporate or exclude extra-framework ligands in the NU-2001 system, a vanadium-based metal–organic framework constructed from the bulky, three-dimensional (3D) linker bicyclo[2.2.2]octane-1,4-dicarboxylic acid (BODCA). This synthetic approach enabled efficient screening of a design space consisting of around 2,700 points through only 55 total reactions. Analysis of the local coordination environment and oxidation state of the vanadium centers suggests that the extra-framework ligands are charge-balancing when incorporated. Comprehensive characterization of both the guest and guest-free phases using X-ray diffraction, adsorption measurements, and X-ray absorption spectroscopy reveals that incorporation of extra-framework ligands alters pore geometry, while also influencing framework stability and flexibility. The combination of thermal stability, redox-active vanadium centers, and additional tunability via selective incorporation of extra-framework ligands in the NU-2001 system warrants further investigation of these materials for important catalysis and separation applications.
Keywords:
metal−organic frameworks
Bayesian optimization
Latin hypercube sampling
vanadium
X-ray diffraction
extra-framework ligands
stability
rigidity
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