Functionalization
of copper carboxylate groups on a series of UiO-66
metal organic framework (MOF) analogues and their corresponding impact
on humid and dry ammonia adsorption behavior were studied. Relative
locations of possible carboxylic acid binding sites for copper on
the MOF analogues were varied on ligand and missing linker defect
sites. Materials after copper incorporation exhibited increased water
vapor and ammonia affinity during isothermal adsorption and breakthrough
experiments, respectively. The introduction of copper markedly increased
ammonia adsorption capacities for all adsorbents possessing carboxyl
binding sites. In particular, the new MOF UiO-66-(COOCu)2 displayed the highest ammonia breakthrough capacities of 6.38 and
6.84 mmol g–1 under dry and humid conditions, respectively,
while retaining crystallinity and porosity. Relative carboxylic acid
site locations were also found to impact sorbent stability, as missing
linker defect functionalized materials degraded under humid conditions
after copper incorporation. Postsynthetic metal insertion provides
a method for adding sites that are analogous to open metal sites while
maintaining good structural stability.
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