Integrated Soft Porosity and Electrical Properties of Conductive-on-Insulating Metal-Organic Framework Nanocrystals

Ming Shui Yao, Ken ichi Otake*, Jiajia Zheng, Masahiko Tsujimoto, Yi Fan Gu, Lu Zheng, Ping Wang, Shivanna Mohana, Mickaele Bonneau, Tomoyuki Koganezawa, Tetsuo Honma, Hirotaka Ashitani, Shogo Kawaguchi, Yoshiki Kubota, Susumu Kitagawa*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

3 Scopus citations

Abstract

A one-stone, two-bird method to integrate the soft porosity and electrical properties of distinct metal–organic frameworks (MOFs) into a single material involves the design of conductive-on-insulating MOF (cMOF-on-iMOF) heterostructures that allow for direct electrical control. Herein, we report the synthesis of cMOF-on-iMOF heterostructures using a seeded layer-by-layer method, in which the sorptive iMOF core is combined with chemiresistive cMOF shells. The resulting cMOF-on-iMOF heterostructures exhibit enhanced selective sorption of CO2 compared to the pristine iMOF (298 K, 1 bar, S (Figure presented.) from 15.4 of ZIF-7 to 43.2–152.8). This enhancement is attributed to the porous interface formed by the hybridization of both frameworks at the molecular level. Furthermore, owing to the flexible structure of the iMOF core, the cMOF-on-iMOF heterostructures with semiconductive soft porous interfaces demonstrated high flexibility in sensing and electrical “shape memory” toward acetone and CO2. This behavior was observed through the guest-induced structural changes of the iMOF core, as revealed by the operando synchrotron grazing incidence wide-angle X-ray scattering measurements.

Original languageEnglish (US)
Article numbere202303903
JournalAngewandte Chemie - International Edition
Volume62
Issue number35
DOIs
StatePublished - Aug 28 2023

Bibliographical note

Funding Information:
This work was supported by the national natural science foundation of China (21801243), the KAKENHI Grant‐in‐Aid for Scientific Research (S) (JP18H05262, JP22H05005) and (C) (JP22K05128) from the Japan Society of the Promotion of Science (JSPS), and International Research Fellow of JSPS (Postdoctoral Fellowships for Research in Japan (Standard), P18334). Synchrotron X‐ray measurements were supported by the Japan Synchrotron Radiation Research Institute (JASRI) (Proposal No. 2020A1628, 2020A1819, 2021A1542, 2021A1683, 2021B1886, 2021B1950). We thank the iCeMS analysis center for the access to the analytical instruments. We warmly thank Ms. M. Gochomori for her contributions to the ligand synthesis, as well as Renjun Zhang, Meng Wang, Haiyan Jiang and Jianze Xiao for the fruitful discussions and help with manuscript editing.

Publisher Copyright:
© 2023 Wiley-VCH GmbH.

Keywords

  • Conductivity
  • Metal–Organic Frameworks
  • Operando
  • Shape Memory
  • Soft Porosity

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry

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