Conspectus
Metal–organic
frameworks (MOFs) are a huge, rapidly growing
class of crystalline, porous materials that consist of inorganic nodes
linked by organic struts. Offering the advantages of thermal stability
combined with high densities of accessible reactive sites, some MOFs
are good candidate materials for applications in catalysis and separations.
Such MOFs include those with nodes that are metal oxide clusters (e.g.,
Zr6O8, Hf6O8, and Zr12O22) and long rods (e.g., [Al(OH)]
n
). These nanostructured metal oxides are often compared
with bulk metal oxides, but they are in essence different because
their structures are not the same and because the MOFs have a high
degree of uniformity, offering the prospect of a deep understanding
of reactivity that is barely attainable for most bulk metal oxides
because of their surface heterogeneity. This prospect is being realized
as it has become evident that adventitious components on MOF node
surfaces, besides the linkers, are crucial. These ligands arise from
modulators, solvents, or products of solvent decomposition in MOF
synthesis solutions, and because they are minor components that are
often irregularly placed on defects, they may not show up in X-ray
diffraction (XRD) crystal structures. Hydroxyl groups on the nodes
(like those on bulk metal oxides) are regarded as native functional
groups arising from solvent water, but they may barely be present
initially, with common ligands instead being formate and acetate formed
from modulators formic acid and acetic acid. (Formate also arises
from the decomposition of dimethylformamide (DMF) solvent.) Replacement
and control of the node ligands is facilitated by postsynthesis reactions
(e.g., with alcohols or aqueous HCl/H2SO4 solutions)
or as a result of high-temperature decomposition. In catalysis, adventitious
node ligands can be (a) reaction inhibitors that block active sites
on the nodes (e.g., formate blocking Zr, Hf, or Al Lewis acid sites);
(b) reaction intermediates (e.g., ethoxy in ethanol dehydration);
or (c) active sites themselves (e.g., terminal OH groups in tert-butyl alcohol (TBA) dehydration). Surprisingly, in
view of the catalytic importance of such ligands on bulk metal oxides,
their subtle chemistry on MOF nodes is only recently being determined.
We describe (1) methods for identifying and quantifying node ligands
(especially by IR spectroscopy and by 1H NMR spectroscopy
of MOFs digested in NaOH/D2O solutions); (2) node ligand
surface chemistry expressed as reaction networks; (3) catalysis, with
mechanisms and energetics determined by density functional theory
(DFT) and spectroscopy; and (4) MOF unzipping by reactions of linker
carboxylate ligands with reactants such as alcohols that break node-linker
bonds, a cause of catalyst deactivation and also an indicator of node-linker
bond strength and MOF stability.