TY - JOUR
T1 - Regioselective Atomic Layer Deposition in Metal-Organic Frameworks Directed by Dispersion Interactions
AU - Gallington, Leighanne C.
AU - Kim, In Soo
AU - Liu, Wei Guang
AU - Yakovenko, Andrey A.
AU - Platero-Prats, Ana E.
AU - Li, Zhanyong
AU - Wang, Timothy C.
AU - Hupp, Joseph T.
AU - Farha, Omar K.
AU - Truhlar, Donald G.
AU - Martinson, Alex B.F.
AU - Chapman, Karena W.
N1 - Funding Information:
This work was supported as part of the Inorganometallic Catalysis Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences, under Award No. DESC0012702. It used resources of the Advanced Photon Source, a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. A.E.P.-P. acknowledges
Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/10/19
Y1 - 2016/10/19
N2 - The application of atomic layer deposition (ALD) to metal-organic frameworks (MOFs) offers a promising new approach to synthesize designer functional materials with atomic precision. While ALD on flat substrates is well established, the complexity of the pore architecture and surface chemistry in MOFs present new challenges. Through in situ synchrotron X-ray powder diffraction, we visualize how the deposited atoms are localized and redistribute within the MOF during ALD. We demonstrate that the ALD is regioselective, with preferential deposition of oxy-Zn(II) species within the small pores of NU-1000. Complementary density functional calculations indicate that this startling regioselectivity is driven by dispersion interactions associated with the preferential adsorption sites for the organometallic precursors prior to reaction.
AB - The application of atomic layer deposition (ALD) to metal-organic frameworks (MOFs) offers a promising new approach to synthesize designer functional materials with atomic precision. While ALD on flat substrates is well established, the complexity of the pore architecture and surface chemistry in MOFs present new challenges. Through in situ synchrotron X-ray powder diffraction, we visualize how the deposited atoms are localized and redistribute within the MOF during ALD. We demonstrate that the ALD is regioselective, with preferential deposition of oxy-Zn(II) species within the small pores of NU-1000. Complementary density functional calculations indicate that this startling regioselectivity is driven by dispersion interactions associated with the preferential adsorption sites for the organometallic precursors prior to reaction.
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U2 - 10.1021/jacs.6b08711
DO - 10.1021/jacs.6b08711
M3 - Article
AN - SCOPUS:84992197943
VL - 138
SP - 13513
EP - 13516
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 41
ER -