Tunable coordinative defects in UHM-3 surface-mounted MOFs for gas adsorption and separation: A combined experimental and theoretical study

Zhengbang Wang, Hikmet Sezen, Jinxuan Liu, Chengwu Yang, Stephanie E. Roggenbuck, Katharina Peikert, Michael Fröba, Andreas Mavrantonakis, Barbara Supronowicz, Thomas Heine, Hartmut Gliemann, Christof Wöll

Research output: Contribution to journalArticlepeer-review

27 Scopus citations


The metal organic framework (MOF) UHM-3, constructed with Cu(II)-paddle wheel-type nodes and a new tetracarboxylic acid linker, 5,5′-(dimethylsilanediyl)diisophthalate, has a close-packed alignment of open Cu(II) sites which are of interest for applications in gas storage and separation. Here, we first report on the growth of oriented, homogeneous and virtually defect-free (below 1%) UHM-3 MOF thin films on a solid substrate using a room-temperature liquid phase epitaxy (LPE) method. Thermal postsynthetic treatment allowed to induce Cu(I) defect sites in a controlled fashion. The interaction of CO and CO2 with the Cu(II) and Cu(I) sites was then studied using X-ray photoelectron spectroscopy (XPS) and IR-spectroscopy. The binding energy of these two species was determined using temperature-induced desorption. The interaction between the guest molecules and the Cu(I) and Cu(II) sites were also analyzed using density-functional theory (DFT). Surprisingly, both experiment and theory show that the binding energy of CO2 to Cu(I) and Cu(II) sites are essentially identical, in pronounced contrast to CO, which binds much stronger to Cu(I).

Original languageEnglish (US)
Pages (from-to)53-60
Number of pages8
JournalMicroporous and Mesoporous Materials
StatePublished - May 1 2015

Bibliographical note

Funding Information:
Financial support by Deutsche Forschungsgemeinschaft (DFG) within the Priority Program Metal−Organic Frameworks (SPP 1362) is gratefully acknowledged. Z. Wang and C. Yang thank the Chinese Scholarship Council (CSC No. 2011695014) for their financial support. Advice and experimental help from Dr. S. Grosjean and Prof. S. Braese (Institute for Organic Chemistry, KIT) is greatly appreciated.

Publisher Copyright:
© 2015 Elsevier Inc. All rights reserved.

Copyright 2015 Elsevier B.V., All rights reserved.


  • Defect
  • Density-functional theory
  • Frameworks
  • Metaleorganic frameworks
  • Surface mounted metaleorganic
  • Thin films

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