TY - JOUR
T1 - Atomic Layer Deposition in a Metal-Organic Framework
T2 - Synthesis, Characterization, and Performance of a Solid Acid
AU - Rimoldi, Martino
AU - Bernales, Varinia
AU - Borycz, Joshua
AU - Vjunov, Aleksei
AU - Gallington, Leighanne C.
AU - Platero-Prats, Ana E.
AU - Kim, I. S.
AU - Fulton, John L.
AU - Martinson, A. B.F.
AU - Lercher, Johannes A.
AU - Chapman, Karena W.
AU - Cramer, Christopher J.
AU - Gagli, Laura
AU - Hupp, Joseph T.
AU - Farha, Omar K.
N1 - Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/2/14
Y1 - 2017/2/14
N2 - NU-1000, a zirconium-based metal-organic framework (MOF) featuring mesoporous channels, has been postsynthetically metalated via atomic layer deposition in a MOF (AIM) employing dimethylaluminum iso-propoxide ([AlMe2OiPr]2, DMAI), a milder precursor than widely used trimethylaluminum (AlMe3, TMA). The aluminum-modified NU-1000 (Al-NU-1000) has been characterized with a comprehensive suite of techniques that points to the formation of aluminum oxide clusters well dispersed through the framework and stabilized by confinement within small pores intrinsic to the NU-1000 structure. Experimental evidence allows for identification of spectroscopic similarities between Al-NU-1000 and γ-Al2O3. Density functional theory modeling provides structures and simulated spectra, the relevance of which can be assessed via comparison to experimental IR and EXAFS data. The catalytic performance of Al-NU-1000 has been benchmarked against γ-Al2O3, with promising results in terms of selectivity.
AB - NU-1000, a zirconium-based metal-organic framework (MOF) featuring mesoporous channels, has been postsynthetically metalated via atomic layer deposition in a MOF (AIM) employing dimethylaluminum iso-propoxide ([AlMe2OiPr]2, DMAI), a milder precursor than widely used trimethylaluminum (AlMe3, TMA). The aluminum-modified NU-1000 (Al-NU-1000) has been characterized with a comprehensive suite of techniques that points to the formation of aluminum oxide clusters well dispersed through the framework and stabilized by confinement within small pores intrinsic to the NU-1000 structure. Experimental evidence allows for identification of spectroscopic similarities between Al-NU-1000 and γ-Al2O3. Density functional theory modeling provides structures and simulated spectra, the relevance of which can be assessed via comparison to experimental IR and EXAFS data. The catalytic performance of Al-NU-1000 has been benchmarked against γ-Al2O3, with promising results in terms of selectivity.
UR - http://www.scopus.com/inward/record.url?scp=85012994933&partnerID=8YFLogxK
U2 - 10.1021/acs.chemmater.6b03880
DO - 10.1021/acs.chemmater.6b03880
M3 - Article
AN - SCOPUS:85012994933
SN - 0897-4756
VL - 29
SP - 1058
EP - 1068
JO - Chemistry of Materials
JF - Chemistry of Materials
IS - 3
ER -