Abstract

Hierarchical heteronuclear metal-organic gels (MOGs) based on iron (Fe) and aluminium (Al) metal-organic framework (MOF) backbones bridged by tri-carboxylate ligands have firstly been synthesized by simple solvothermal method. Monometallic MOGs based on Fe or Al give homogenous monoliths, which have been tuned by introduction of heterogeneity in the system (mismatched growth). The developed gels demonstrate that surface areas, pore volumes and pore sizes can be readily tuned by optimizing heterogeneity. The work also elaborates effect of heterogeneity on size of MOG particles which increase substantially with increasing heterogeneity as well as obtaining mixed valence sites in the gels. High surface areas (1861 m2/g) and pore volumes (9.737 cc/g) were obtained for heterogeneous gels (0.5Fe-0.5Al). The large uptakes of dye molecules (290 mg/g rhodamine B and 265 mg/g methyl orange) with fast sorption kinetics in both neutral and acidic mediums show good stability and accessibility of MOG channels (micro and meso-/macropores), further demonstrating their potential applications in catalysis and sorption of large molecules.

Highlights

  • Areas, tunable porosities, inherent structure retention, low densities, inherently present open metal sites and large channels for mass transfer, sorption and catalysis[27,32]

  • Several monometallic and bimetallic MOAs and MOXs have been synthesized with different concentrations of metals such as Fe-BTC (MOA-1 and MOX-1), 0.75Fe-0.25Al-BTC (MOA-2 and MOX-2), 0.5Fe-0.5Al-BTC (MOA-3 and MOX-3), 0.25Fe-0.75Al-BTC (MOA-4 and MOX-4) and Al-BTC (MOA-5 and MOX-5), respectively

  • Monometallic system (Fe or Al) leads to homogenous monoliths where growth of metal-organic frameworks (MOF) chains is only perturbed upon decrease in reactant concentrations which results in increased crytallinity in the product

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Summary

Results

Several monometallic and bimetallic MOAs and MOXs have been synthesized with different concentrations of metals such as Fe-BTC (MOA-1 and MOX-1), 0.75Fe-0.25Al-BTC (MOA-2 and MOX-2), 0.5Fe-0.5Al-BTC (MOA-3 and MOX-3), 0.25Fe-0.75Al-BTC (MOA-4 and MOX-4) and Al-BTC (MOA-5 and MOX-5), respectively. Mixed metal MOXs show considerably less uptake of N2 in comparison to their MOA counterparts (Fig. 3d) which clearly suggest destruction of channels in MOGs upon drying in air This fact is further proved by pore size distribution of MOXs shown in Fig. 3e where all the pores are in the range of 1-4 nm which is due to shrinkage of meso-/macropores towards microporous nature. (f) Comparison of N2 sorption for MOA-3 and MOX-3 and inset shows difference in pore size distribution of respective MOGs. N confirm the presence of all species in the synthesized MOGs as shown in Fig. 4b and Figure S9a,b.

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