Metal nanocrystals embedded in single nanocrystals of MOFs give unusual selectivity as heterogeneous catalysts

Kyungsu Na; Kyung Min Choi; Omar M. Yaghi; Gabor A. Somorjai

doi:10.1021/nl503007h

Metal nanocrystals embedded in single nanocrystals of MOFs give unusual selectivity as heterogeneous catalysts

Kyungsu Na
, Kyung Min Choi
, Omar M. Yaghi^*
, Gabor A. Somorjai

^*Corresponding author for this work

King Fahd University of Petroleum & Minerals

Research output: Contribution to journal › Article › peer-review

235 Scopus citations

Abstract

The growth of nanocrystalline metal-organic frameworks (nMOFs) around metal nanocrystals (NCs) is useful in controlling the chemistry and metric of metal NCs. In this Letter, we show rare examples of nMOFs grown in monocrystalline form around metal NCs. Specifically, Pt NCs were subjected to reactions yielding Zr(IV) nMOFs [Zr₆O₄(OH)₄(fumarate)₆, MOF-801; Zr₆O₄(OH)₄(BDC)₆ (BDC = 1,4-benzenedicarboxylate), UiO-66; Zr₆O₄(OH)₄(BPDC)₆ (BPDC = 4,4′-biphenyldicarboxylate), UiO-67] as a single crystal within which the Pt NCs are embedded. These constructs (Pt⊂nMOF)_nanocrystal are found to be active in gas-phase hydrogenative conversion of methylcyclopentane (MCP) and give unusual product selectivity. The Pt⊂nUiO-66 shows selectivity to C₆-cyclic hydrocarbons such as cyclohexane and benzene that takes place with 100 °C lower temperature than the standard reaction (Pt-on-SiO₂). We observe a pore size effect in the nMOF series where the small pore of Pt⊂nMOF-801 does not produce the same products, while the larger pore Pt⊂nUiO-67 catalyst provides the same products but with different selectivity. The (Pt⊂nMOF)_nanocrystal spent catalyst is found to maintain the original crystallinity, and be recyclable without any byproduct residues.

Original language	English
Pages (from-to)	5979-5983
Number of pages	5
Journal	Nano Letters
Volume	14
Issue number	10
DOIs	https://doi.org/10.1021/nl503007h
State	Published - 8 Oct 2014

Bibliographical note

Publisher Copyright:
© 2014 American Chemical Society.

Keywords

Metal-organic Framework
heterogeneous catalyst
isomerization
metal nanocrystal
methylcyclopentane

ASJC Scopus subject areas

Bioengineering
General Chemistry
General Materials Science
Condensed Matter Physics
Mechanical Engineering

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10.1021/nl503007h

Cite this

@article{8970885fee4f4a85b805324f1bf3ec3f,

title = "Metal nanocrystals embedded in single nanocrystals of MOFs give unusual selectivity as heterogeneous catalysts",

abstract = "The growth of nanocrystalline metal-organic frameworks (nMOFs) around metal nanocrystals (NCs) is useful in controlling the chemistry and metric of metal NCs. In this Letter, we show rare examples of nMOFs grown in monocrystalline form around metal NCs. Specifically, Pt NCs were subjected to reactions yielding Zr(IV) nMOFs [Zr6O4(OH)4(fumarate)6, MOF-801; Zr6O4(OH)4(BDC)6 (BDC = 1,4-benzenedicarboxylate), UiO-66; Zr6O4(OH)4(BPDC)6 (BPDC = 4,4′-biphenyldicarboxylate), UiO-67] as a single crystal within which the Pt NCs are embedded. These constructs (Pt⊂nMOF)nanocrystal are found to be active in gas-phase hydrogenative conversion of methylcyclopentane (MCP) and give unusual product selectivity. The Pt⊂nUiO-66 shows selectivity to C6-cyclic hydrocarbons such as cyclohexane and benzene that takes place with 100 °C lower temperature than the standard reaction (Pt-on-SiO2). We observe a pore size effect in the nMOF series where the small pore of Pt⊂nMOF-801 does not produce the same products, while the larger pore Pt⊂nUiO-67 catalyst provides the same products but with different selectivity. The (Pt⊂nMOF)nanocrystal spent catalyst is found to maintain the original crystallinity, and be recyclable without any byproduct residues.",

keywords = "Metal-organic Framework, heterogeneous catalyst, isomerization, metal nanocrystal, methylcyclopentane",

author = "Kyungsu Na and Choi, \{Kyung Min\} and Yaghi, \{Omar M.\} and Somorjai, \{Gabor A.\}",

note = "Publisher Copyright: {\textcopyright} 2014 American Chemical Society.",

year = "2014",

month = oct,

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doi = "10.1021/nl503007h",

language = "English",

volume = "14",

pages = "5979--5983",

journal = "Nano Letters",

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publisher = "American Chemical Society",

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T1 - Metal nanocrystals embedded in single nanocrystals of MOFs give unusual selectivity as heterogeneous catalysts

AU - Na, Kyungsu

AU - Choi, Kyung Min

AU - Yaghi, Omar M.

AU - Somorjai, Gabor A.

PY - 2014/10/8

Y1 - 2014/10/8

N2 - The growth of nanocrystalline metal-organic frameworks (nMOFs) around metal nanocrystals (NCs) is useful in controlling the chemistry and metric of metal NCs. In this Letter, we show rare examples of nMOFs grown in monocrystalline form around metal NCs. Specifically, Pt NCs were subjected to reactions yielding Zr(IV) nMOFs [Zr6O4(OH)4(fumarate)6, MOF-801; Zr6O4(OH)4(BDC)6 (BDC = 1,4-benzenedicarboxylate), UiO-66; Zr6O4(OH)4(BPDC)6 (BPDC = 4,4′-biphenyldicarboxylate), UiO-67] as a single crystal within which the Pt NCs are embedded. These constructs (Pt⊂nMOF)nanocrystal are found to be active in gas-phase hydrogenative conversion of methylcyclopentane (MCP) and give unusual product selectivity. The Pt⊂nUiO-66 shows selectivity to C6-cyclic hydrocarbons such as cyclohexane and benzene that takes place with 100 °C lower temperature than the standard reaction (Pt-on-SiO2). We observe a pore size effect in the nMOF series where the small pore of Pt⊂nMOF-801 does not produce the same products, while the larger pore Pt⊂nUiO-67 catalyst provides the same products but with different selectivity. The (Pt⊂nMOF)nanocrystal spent catalyst is found to maintain the original crystallinity, and be recyclable without any byproduct residues.

AB - The growth of nanocrystalline metal-organic frameworks (nMOFs) around metal nanocrystals (NCs) is useful in controlling the chemistry and metric of metal NCs. In this Letter, we show rare examples of nMOFs grown in monocrystalline form around metal NCs. Specifically, Pt NCs were subjected to reactions yielding Zr(IV) nMOFs [Zr6O4(OH)4(fumarate)6, MOF-801; Zr6O4(OH)4(BDC)6 (BDC = 1,4-benzenedicarboxylate), UiO-66; Zr6O4(OH)4(BPDC)6 (BPDC = 4,4′-biphenyldicarboxylate), UiO-67] as a single crystal within which the Pt NCs are embedded. These constructs (Pt⊂nMOF)nanocrystal are found to be active in gas-phase hydrogenative conversion of methylcyclopentane (MCP) and give unusual product selectivity. The Pt⊂nUiO-66 shows selectivity to C6-cyclic hydrocarbons such as cyclohexane and benzene that takes place with 100 °C lower temperature than the standard reaction (Pt-on-SiO2). We observe a pore size effect in the nMOF series where the small pore of Pt⊂nMOF-801 does not produce the same products, while the larger pore Pt⊂nUiO-67 catalyst provides the same products but with different selectivity. The (Pt⊂nMOF)nanocrystal spent catalyst is found to maintain the original crystallinity, and be recyclable without any byproduct residues.

KW - Metal-organic Framework

KW - heterogeneous catalyst

KW - isomerization

KW - metal nanocrystal

KW - methylcyclopentane

UR - https://www.scopus.com/pages/publications/84907865151

U2 - 10.1021/nl503007h

DO - 10.1021/nl503007h

M3 - Article

AN - SCOPUS:84907865151

SN - 1530-6984

VL - 14

SP - 5979

EP - 5983

JO - Nano Letters

JF - Nano Letters

IS - 10

ER -

Metal nanocrystals embedded in single nanocrystals of MOFs give unusual selectivity as heterogeneous catalysts

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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