Bond breakage under pressure in a metal organic framework

Zhi Su; Yu Run Miao; Guanghui Zhang; Jeffrey T. Miller; Kenneth S. Suslick

doi:10.1039/c7sc03786d

Bond breakage under pressure in a metal organic framework

Zhi Su, Yu Run Miao, Guanghui Zhang, Jeffrey T. Miller, Kenneth S. Suslick

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

Abstract

The internal free volume of porous materials diminishes upon mechanical compression, and such volume collapse can have chemical consequences. We report here the endothermic bond breakage in a metal-organic framework (MOF) during compression-induced collapse. Upon bulk compression at 1.9 GPa, the effective number for Zr-O bonds between Zr(iv) ions and carboxylate groups in UiO-66 decreased from 4.0 to 1.9, as determined by EXAFS, and the internal free volume was synchronously collapsed. Consistent with the EXAFS data, IR spectra confirmed conversion of syn-syn bridging carboxylates to monodentate ligation, thus establishing mechanochemical reactions induced by external compression of MOFs. Substantial mechanical energy (∼4 kJ g^-1) was absorbed by UiO-66 nanocrystals during compression, as demonstrated from nanocompression of single crystals (600 nm) in situ during scanning electron microscopy, which establishes the potential application of MOFs as mechanical energy absorbers for hydrostatic and shock compression.

Original language	English (US)
Pages (from-to)	8004-8011
Number of pages	8
Journal	Chemical Science
Volume	8
Issue number	12
DOIs	https://doi.org/10.1039/c7sc03786d
State	Published - 2017

ASJC Scopus subject areas

Chemistry(all)

Online availability

10.1039/c7sc03786d

Library availability

Discover UIUC Full Text

Cite this

@article{ea51eb3edc5240048394c1945bffbc3a,

title = "Bond breakage under pressure in a metal organic framework",

abstract = "The internal free volume of porous materials diminishes upon mechanical compression, and such volume collapse can have chemical consequences. We report here the endothermic bond breakage in a metal-organic framework (MOF) during compression-induced collapse. Upon bulk compression at 1.9 GPa, the effective number for Zr-O bonds between Zr(iv) ions and carboxylate groups in UiO-66 decreased from 4.0 to 1.9, as determined by EXAFS, and the internal free volume was synchronously collapsed. Consistent with the EXAFS data, IR spectra confirmed conversion of syn-syn bridging carboxylates to monodentate ligation, thus establishing mechanochemical reactions induced by external compression of MOFs. Substantial mechanical energy (∼4 kJ g-1) was absorbed by UiO-66 nanocrystals during compression, as demonstrated from nanocompression of single crystals (600 nm) in situ during scanning electron microscopy, which establishes the potential application of MOFs as mechanical energy absorbers for hydrostatic and shock compression.",

author = "Zhi Su and Miao, {Yu Run} and Guanghui Zhang and Miller, {Jeffrey T.} and Suslick, {Kenneth S.}",

note = "Funding Information: We acknowledge funding through the U.S. Navy (MURI N000141210828) and the use of the Frederick Seitz Materials Research Laboratory Central Facilities, UIUC. APS use was supported by the U.S. DOE BES, Contract No. DE-AC02-06CH11357; MRCAT operations are supported by the DOE and the MRCAT member institutions. Z. S. thanks the nancial support from NSF China (No. 21601088) and NSF of Jiangsu Province of China (No. BK20171472). Publisher Copyright: {\textcopyright} 2017 The Royal Society of Chemistry.",

year = "2017",

doi = "10.1039/c7sc03786d",

language = "English (US)",

volume = "8",

pages = "8004--8011",

journal = "Chemical Science",

issn = "2041-6520",

publisher = "Royal Society of Chemistry",

number = "12",

}

TY - JOUR

T1 - Bond breakage under pressure in a metal organic framework

AU - Su, Zhi

AU - Miao, Yu Run

AU - Zhang, Guanghui

AU - Miller, Jeffrey T.

AU - Suslick, Kenneth S.

N1 - Funding Information: We acknowledge funding through the U.S. Navy (MURI N000141210828) and the use of the Frederick Seitz Materials Research Laboratory Central Facilities, UIUC. APS use was supported by the U.S. DOE BES, Contract No. DE-AC02-06CH11357; MRCAT operations are supported by the DOE and the MRCAT member institutions. Z. S. thanks the nancial support from NSF China (No. 21601088) and NSF of Jiangsu Province of China (No. BK20171472). Publisher Copyright: © 2017 The Royal Society of Chemistry.

PY - 2017

Y1 - 2017

N2 - The internal free volume of porous materials diminishes upon mechanical compression, and such volume collapse can have chemical consequences. We report here the endothermic bond breakage in a metal-organic framework (MOF) during compression-induced collapse. Upon bulk compression at 1.9 GPa, the effective number for Zr-O bonds between Zr(iv) ions and carboxylate groups in UiO-66 decreased from 4.0 to 1.9, as determined by EXAFS, and the internal free volume was synchronously collapsed. Consistent with the EXAFS data, IR spectra confirmed conversion of syn-syn bridging carboxylates to monodentate ligation, thus establishing mechanochemical reactions induced by external compression of MOFs. Substantial mechanical energy (∼4 kJ g-1) was absorbed by UiO-66 nanocrystals during compression, as demonstrated from nanocompression of single crystals (600 nm) in situ during scanning electron microscopy, which establishes the potential application of MOFs as mechanical energy absorbers for hydrostatic and shock compression.

AB - The internal free volume of porous materials diminishes upon mechanical compression, and such volume collapse can have chemical consequences. We report here the endothermic bond breakage in a metal-organic framework (MOF) during compression-induced collapse. Upon bulk compression at 1.9 GPa, the effective number for Zr-O bonds between Zr(iv) ions and carboxylate groups in UiO-66 decreased from 4.0 to 1.9, as determined by EXAFS, and the internal free volume was synchronously collapsed. Consistent with the EXAFS data, IR spectra confirmed conversion of syn-syn bridging carboxylates to monodentate ligation, thus establishing mechanochemical reactions induced by external compression of MOFs. Substantial mechanical energy (∼4 kJ g-1) was absorbed by UiO-66 nanocrystals during compression, as demonstrated from nanocompression of single crystals (600 nm) in situ during scanning electron microscopy, which establishes the potential application of MOFs as mechanical energy absorbers for hydrostatic and shock compression.

UR - http://www.scopus.com/inward/record.url?scp=85034748886&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85034748886&partnerID=8YFLogxK

U2 - 10.1039/c7sc03786d

DO - 10.1039/c7sc03786d

M3 - Article

AN - SCOPUS:85034748886

SN - 2041-6520

VL - 8

SP - 8004

EP - 8011

JO - Chemical Science

JF - Chemical Science

IS - 12

ER -

Bond breakage under pressure in a metal organic framework

Abstract

ASJC Scopus subject areas

Online availability

Library availability

Related links

Fingerprint

Cite this