Mesoscopic Constructs of Ordered and Oriented Metal–Organic Frameworks on Plasmonic Silver Nanocrystals

Zhao, Yingbo; Kornienko, Nikolay; Liu, Zheng; Zhu, Chenhui; Asahina, Shunsuke; Kuo, Tsung-Rong; Bao, Wei; Xie, Chenlu; Hexemer, Alexander; Terasaki, Osamu; Yang, Peidong; Yaghi, Omar M.

doi:10.1021/ja512951e

Mesoscopic Constructs of Ordered and Oriented Metal–Organic Frameworks on Plasmonic Silver Nanocrystals

Journal Article · Mon Jan 26 00:00:00 EST 2015 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja512951e· OSTI ID:1832452

Zhao, Yingbo ^[1]; Kornienko, Nikolay ^[1]; Liu, Zheng ^[2]; Zhu, Chenhui ^[3]; Asahina, Shunsuke ^[4]; Kuo, Tsung-Rong ^[1]; Bao, Wei ^[1]; Xie, Chenlu ^[1]; Hexemer, Alexander ^[3]; Terasaki, Osamu ^[5]; Yang, Peidong ^[1]; Yaghi, Omar M. ^[6]

Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Kavli Energy NanoScience Institute, Berkeley, CA (United States)
National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
JEOL Ltd., Tokyo (Japan)
Stockholm Univ. (Sweden); Korea Advanced Inst. Science and Technology (KAIST), Daejeon (Korea, Republic of)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Kavli Energy NanoScience Institute, Berkeley, CA (United States); King Abdulaziz City for Science and Technology, Riyadh (Saudi Arabia)

We enclose octahedral silver nanocrystals (Ag NCs) in metal-organic frameworks (MOFs) to make mesoscopic constructs O_h-nano-Ag$$\subset$$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.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: Suzhou Industrial Park; USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1832452

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 6 Vol. 137; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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