TY - JOUR
T1 - Targeted Single-Site MOF Node Modification
T2 - Trivalent Metal Loading via Atomic Layer Deposition
AU - Kim, In Soo
AU - Borycz, Joshua
AU - Platero-Prats, Ana E.
AU - Tussupbayev, Samat
AU - Wang, Timothy C.
AU - Farha, Omar K.
AU - Hupp, Joseph T.
AU - Gagliardi, Laura
AU - Chapman, Karena W.
AU - Cramer, Christopher J.
AU - Martinson, Alex B.F.
N1 - Publisher Copyright:
© 2015 American Chemical Society.
PY - 2015/7/14
Y1 - 2015/7/14
N2 - Postsynthetic functionalization of metal organic frameworks (MOFs) enables the controlled, high-density incorporation of new atoms on a crystallographically precise framework. Leveraging the broad palette of known atomic layer deposition (ALD) chemistries, ALD in MOFs (AIM) is one such targeted approach to construct diverse, highly functional, few-atom clusters. We here demonstrate the saturating reaction of trimethylindium (InMe3) with the node hydroxyls and ligated water of NU-1000, which takes place without significant loss of MOF crystallinity or internal surface area. We computationally identify the elementary steps by which trimethylated trivalent metal compounds (ALD precursors) react with this Zr-based MOF node to generate a uniform and well characterized new surface layer on the node itself, and we predict a final structure that is fully consistent with experimental X-ray pair distribution function (PDF) analysis. We further demonstrate tunable metal loading through controlled number density of the reactive handles (-OH and -OH2) achieved through node dehydration at elevated temperatures.
AB - Postsynthetic functionalization of metal organic frameworks (MOFs) enables the controlled, high-density incorporation of new atoms on a crystallographically precise framework. Leveraging the broad palette of known atomic layer deposition (ALD) chemistries, ALD in MOFs (AIM) is one such targeted approach to construct diverse, highly functional, few-atom clusters. We here demonstrate the saturating reaction of trimethylindium (InMe3) with the node hydroxyls and ligated water of NU-1000, which takes place without significant loss of MOF crystallinity or internal surface area. We computationally identify the elementary steps by which trimethylated trivalent metal compounds (ALD precursors) react with this Zr-based MOF node to generate a uniform and well characterized new surface layer on the node itself, and we predict a final structure that is fully consistent with experimental X-ray pair distribution function (PDF) analysis. We further demonstrate tunable metal loading through controlled number density of the reactive handles (-OH and -OH2) achieved through node dehydration at elevated temperatures.
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U2 - 10.1021/acs.chemmater.5b01560
DO - 10.1021/acs.chemmater.5b01560
M3 - Article
AN - SCOPUS:84937039409
SN - 0897-4756
VL - 27
SP - 4772
EP - 4778
JO - Chemistry of Materials
JF - Chemistry of Materials
IS - 13
ER -