TY - JOUR
T1 - Mesoscopic constructs of ordered and oriented metal-organic frameworks on plasmonic silver nanocrystals
AU - Zhao, Yingbo
AU - Kornienko, Nikolay
AU - Liu, Zheng
AU - Zhu, Chenhui
AU - Asahina, Shunsuke
AU - Kuo, Tsung Rong
AU - Bao, Wei
AU - Xie, Chenlu
AU - Hexemer, Alexander
AU - Terasaki, Osamu
AU - Yang, Peidong
AU - Yaghi, Omar M.
N1 - Publisher Copyright:
© 2015 American Chemical Society.
PY - 2015/2/18
Y1 - 2015/2/18
N2 - We enclose octahedral silver nanocrystals (Ag NCs) in metal-organic frameworks (MOFs) to make mesoscopic constructs Oh-nano-Ag⊂MOF in which the interface between the Ag and the MOF is pristine and the MOF is ordered (crystalline) and oriented on the Ag NCs. This is achieved by atomic layer deposition of aluminum oxide on Ag NCs and addition of a tetra-topic porphyrin-based linker, 4,4′,4″,4⌄-(porphyrin-5,10,15,20-tetrayl)tetrabenzoic acid (H4TCPP), to react with alumina and make MOF [Al2(OH)2TCPP] enclosures around Ag NCs. Alumina thickness is precisely controlled from 0.1 to 3 nm, thus allowing control of the MOF thickness from 10 to 50 nm. Electron microscopy and grazing angle X-ray diffraction confirm the order and orientation of the MOF by virtue of the porphyrin units being perpendicular to the planes of the Ag. We use surface-enhanced Raman spectroscopy to directly track the metalation process on the porphyrin and map the distribution of the metalated and unmetalated linkers on a single-nanoparticle level.
AB - We enclose octahedral silver nanocrystals (Ag NCs) in metal-organic frameworks (MOFs) to make mesoscopic constructs Oh-nano-Ag⊂MOF in which the interface between the Ag and the MOF is pristine and the MOF is ordered (crystalline) and oriented on the Ag NCs. This is achieved by atomic layer deposition of aluminum oxide on Ag NCs and addition of a tetra-topic porphyrin-based linker, 4,4′,4″,4⌄-(porphyrin-5,10,15,20-tetrayl)tetrabenzoic acid (H4TCPP), to react with alumina and make MOF [Al2(OH)2TCPP] enclosures around Ag NCs. Alumina thickness is precisely controlled from 0.1 to 3 nm, thus allowing control of the MOF thickness from 10 to 50 nm. Electron microscopy and grazing angle X-ray diffraction confirm the order and orientation of the MOF by virtue of the porphyrin units being perpendicular to the planes of the Ag. We use surface-enhanced Raman spectroscopy to directly track the metalation process on the porphyrin and map the distribution of the metalated and unmetalated linkers on a single-nanoparticle level.
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U2 - 10.1021/ja512951e
DO - 10.1021/ja512951e
M3 - Article
AN - SCOPUS:84923253093
SN - 0002-7863
VL - 137
SP - 2199
EP - 2202
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 6
ER -