Title: Bridging Zirconia Nodes within a Metal–Organic Framework via Catalytic Ni-Hydroxo Clusters to Form Heterobimetallic Nanowires

Abstract

Metal-organic frameworks (MOFs), with their well-ordered pore networks and tunable surface chemistries, offer a versatile platform for preparing well-defined nanostructures wherein functionality such as catalysis can be incorporated. Notably, atomic layer deposition (ALD) in MOFs has recently emerged as a versatile approach to functionalize MOF surfaces with a wide variety of catalytic metal-oxo species. Understanding the structure of newly deposited species and how they are tethered within the MOF is critical to understanding how these components couple to govern the active material properties. By combining local and long-range structure probes, including X-ray absorption spectroscopy, pair distribution function analysis and difference envelope density analysis, with electron microscopy imag-ing and computational modeling, we resolve the precise atomic structure of metal-oxo species deposited in the MOF NU-1000 through ALD. These analyses demonstrate that deposition of NiO_xH_y clusters occurs selectively within the smallest pores of NU-1000, between the zirconia nodes, serving to connect these nodes along the c-direction to yield hetero-bimetallic metal-oxo nanowires. Finally, this bridging motif perturbs the NU-1000 framework structure, drawing the zirconia nodes closer together, and also underlies the sintering-resistance of these clusters during the hydrogenation of light olefins.

Authors:

Platero-Prats, Ana E.  ^[1];

• Search DOE PAGES for author "Platero-Prats, Ana E."
• Search DOE PAGES for ORCID "0000-0002-2248-2739"

League, Aaron B. ^[2]; Bernales, Varinia ^[2]; Ye, Jingyun ^[2]; Gallington, Leighanne C.  ^[1];

• Search DOE PAGES for author "Gallington, Leighanne C."
• Search DOE PAGES for ORCID "0000-0002-0383-7522"

Vjunov, Aleksei ^[3]; Schweitzer, Neil M. ^[4]; Li, Zhanyong  ^[5];

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• Search DOE PAGES for ORCID "0000-0002-3230-5955"

Zheng, Jian  ^[3];

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• Search DOE PAGES for ORCID "0000-0003-2054-9482"

Mehdi, B. Layla ^[6]; Stevens, Andrew J. ^[3]; Dohnalkova, Alice ^[7]; Balasubramanian, Mahalingam ^[1]; Farha, Omar K.  ^[8];

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• Search DOE PAGES for ORCID "0000-0002-9904-9845"

Hupp, Joseph T.  ^[5];

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• Search DOE PAGES for ORCID "0000-0003-3982-9812"

Browning, Nigel D. ^[9]; Fulton, John L. ^[3]; Camaioni, Donald M. ^[3]; Lercher, Johannes A.  ^[10];

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• Search DOE PAGES for ORCID "0000-0002-2495-1404"

Truhlar, Donald G.  ^[2]

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• Search DOE PAGES for ORCID "0000-0002-7742-7294"

more »; Gagliardi, Laura  ^[2];

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• Search DOE PAGES for ORCID "0000-0001-5227-1396"

Cramer, Christopher J.  ^[2];

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• Search DOE PAGES for ORCID "0000-0001-5048-1859"

Chapman, Karena W.  ^[1]

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• Search DOE PAGES for ORCID "0000-0002-8725-5633"

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+ Show Author Affiliations

1. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS), X-ray Science Division
2. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry, Minnesota Supercomputing Inst. and Chemical Theory Center
3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Inst. for Integrated Catalysis
4. Northwestern Univ., Evanston, IL (United States). Dept. of Chemical and Biological Engineering
5. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
6. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical and Computational Science Directorate
7. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
8. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry; King Abdulaziz Univ., Jeddah (Saudi Arabia). Dept. of Chemistry
9. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical and Computational Science Directorate; Univ. of Washington, Seattle, WA (United States). Dept. of Materials Science and Engineering
10. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Inst. for Integrated Catalysis; Technische Univ. Munchen, Garching (Germany). Dept. of Chemistry and Catalysis Research Inst.

Publication Date:

Tue Jul 11 00:00:00 EDT 2017

Research Org.:

Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC); Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)

OSTI Identifier:

1398808

Grant/Contract Number:  

AC02-06CH11357; SC0012702; AC05-76RL01830

Resource Type:

Accepted Manuscript

Journal Name:

Journal of the American Chemical Society

Additional Journal Information:

Journal Volume: 139; Journal Issue: 30; Journal ID: ISSN 0002-7863

Publisher:

American Chemical Society (ACS)

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE