Impact of Synthesis Parameters on the Formation of Defects in HKUST-1

Wenhua Zhang; Max Kauer; Penghu Guo; Sebastian Kunze; Stefan Cwik; Martin Muhler; Yuemin Wang; Konstantin Epp; Gregor Kieslich; Roland A. Fischer

doi:10.1002/ejic.201601239

Impact of Synthesis Parameters on the Formation of Defects in HKUST-1

Wenhua Zhang
, Max Kauer
, Penghu Guo
, Sebastian Kunze
, Stefan Cwik
, Martin Muhler
, Yuemin Wang
, Konstantin Epp
, Gregor Kieslich
, Roland A. Fischer

Chair of Inorganic and Organometallic Chemistry

Max-Planck-lnstitut für Kohlenforschung
Humanoid Technologies Lab (H2T)
Technical University of Munich

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

53 Scopus citations

Abstract

By employing various synthetic conditions, such as Cu(NO₃)₂·3H₂O and Cu(BF₄)₂·6H₂O as copper ion sources and different solvents, defect-engineered analogues of metal–organic framework (MOF) [Cu₃(BTC)₂] (HKUST-1; BTC = 1,3,5-benzenetricarboxylate) with isophthalate (IP) incorporation (DEMOFs) were synthesised and characterised by powder XRD, SEM, IR spectroscopy, thermogravimetric analysis, NMR spectroscopy and N₂sorption. The results show that the choice of counter ions impacts the properties of the samples especially at high concentrations of IP. The combination of DMF and Cu(BF₄)₂·6H₂O turns out to be superior for DEMOFs with IP incorporation up to 25 %. Ultrahigh-vacuum IR spectra recorded upon CO adsorption together with the results of X-ray photoelectron spectroscopic studies show the generation of coordinatively unsaturated Cu⁺sites. The results suggest the presence of two different defect types, that is, missing-linker defects and missing paddlewheels for high concentrations of IP.

Original language	English
Pages (from-to)	925-931
Number of pages	7
Journal	European Journal of Inorganic Chemistry
Volume	2017
Issue number	5
DOIs	https://doi.org/10.1002/ejic.201601239
State	Published - 2017

Keywords

Carboxylate ligands
Copper
Defect engineering
Metal–organic frameworks
Solvothermal synthesis

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10.1002/ejic.201601239

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@article{9630524c93854677ad36eb1b8c4bc035,

title = "Impact of Synthesis Parameters on the Formation of Defects in HKUST-1",

abstract = "By employing various synthetic conditions, such as Cu(NO3)2·3H2O and Cu(BF4)2·6H2O as copper ion sources and different solvents, defect-engineered analogues of metal–organic framework (MOF) [Cu3(BTC)2] (HKUST-1; BTC = 1,3,5-benzenetricarboxylate) with isophthalate (IP) incorporation (DEMOFs) were synthesised and characterised by powder XRD, SEM, IR spectroscopy, thermogravimetric analysis, NMR spectroscopy and N2sorption. The results show that the choice of counter ions impacts the properties of the samples especially at high concentrations of IP. The combination of DMF and Cu(BF4)2·6H2O turns out to be superior for DEMOFs with IP incorporation up to 25 \%. Ultrahigh-vacuum IR spectra recorded upon CO adsorption together with the results of X-ray photoelectron spectroscopic studies show the generation of coordinatively unsaturated Cu+sites. The results suggest the presence of two different defect types, that is, missing-linker defects and missing paddlewheels for high concentrations of IP.",

keywords = "Carboxylate ligands, Copper, Defect engineering, Metal–organic frameworks, Solvothermal synthesis",

author = "Wenhua Zhang and Max Kauer and Penghu Guo and Sebastian Kunze and Stefan Cwik and Martin Muhler and Yuemin Wang and Konstantin Epp and Gregor Kieslich and Fischer, \{Roland A.\}",

note = "Publisher Copyright: {\textcopyright} 2017 WILEY-VCH Verlag GmbH \& Co. KGaA, Weinheim",

year = "2017",

doi = "10.1002/ejic.201601239",

language = "English",

volume = "2017",

pages = "925--931",

journal = "European Journal of Inorganic Chemistry",

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}

TY - JOUR

T1 - Impact of Synthesis Parameters on the Formation of Defects in HKUST-1

AU - Zhang, Wenhua

AU - Kauer, Max

AU - Guo, Penghu

AU - Kunze, Sebastian

AU - Cwik, Stefan

AU - Muhler, Martin

AU - Wang, Yuemin

AU - Epp, Konstantin

AU - Kieslich, Gregor

AU - Fischer, Roland A.

PY - 2017

Y1 - 2017

N2 - By employing various synthetic conditions, such as Cu(NO3)2·3H2O and Cu(BF4)2·6H2O as copper ion sources and different solvents, defect-engineered analogues of metal–organic framework (MOF) [Cu3(BTC)2] (HKUST-1; BTC = 1,3,5-benzenetricarboxylate) with isophthalate (IP) incorporation (DEMOFs) were synthesised and characterised by powder XRD, SEM, IR spectroscopy, thermogravimetric analysis, NMR spectroscopy and N2sorption. The results show that the choice of counter ions impacts the properties of the samples especially at high concentrations of IP. The combination of DMF and Cu(BF4)2·6H2O turns out to be superior for DEMOFs with IP incorporation up to 25 %. Ultrahigh-vacuum IR spectra recorded upon CO adsorption together with the results of X-ray photoelectron spectroscopic studies show the generation of coordinatively unsaturated Cu+sites. The results suggest the presence of two different defect types, that is, missing-linker defects and missing paddlewheels for high concentrations of IP.

AB - By employing various synthetic conditions, such as Cu(NO3)2·3H2O and Cu(BF4)2·6H2O as copper ion sources and different solvents, defect-engineered analogues of metal–organic framework (MOF) [Cu3(BTC)2] (HKUST-1; BTC = 1,3,5-benzenetricarboxylate) with isophthalate (IP) incorporation (DEMOFs) were synthesised and characterised by powder XRD, SEM, IR spectroscopy, thermogravimetric analysis, NMR spectroscopy and N2sorption. The results show that the choice of counter ions impacts the properties of the samples especially at high concentrations of IP. The combination of DMF and Cu(BF4)2·6H2O turns out to be superior for DEMOFs with IP incorporation up to 25 %. Ultrahigh-vacuum IR spectra recorded upon CO adsorption together with the results of X-ray photoelectron spectroscopic studies show the generation of coordinatively unsaturated Cu+sites. The results suggest the presence of two different defect types, that is, missing-linker defects and missing paddlewheels for high concentrations of IP.

KW - Carboxylate ligands

KW - Copper

KW - Defect engineering

KW - Metal–organic frameworks

KW - Solvothermal synthesis

UR - https://www.scopus.com/pages/publications/85011995000

U2 - 10.1002/ejic.201601239

DO - 10.1002/ejic.201601239

M3 - Article

AN - SCOPUS:85011995000

SN - 1434-1948

VL - 2017

SP - 925

EP - 931

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 5

ER -

Impact of Synthesis Parameters on the Formation of Defects in HKUST-1

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