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

doi:10.1002/anie.202303903

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

Chemistry

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

9 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 language	English (US)
Article number	e202303903
Journal	Angewandte Chemie - International Edition
Volume	62
Issue number	35
DOIs	https://doi.org/10.1002/anie.202303903
State	Published - 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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10.1002/anie.202303903

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Yao, M. S., Otake, K. I., Zheng, J., Tsujimoto, M., Gu, Y. F., Zheng, L., Wang, P., Mohana, S., Bonneau, M., Koganezawa, T., Honma, T., Ashitani, H., Kawaguchi, S., Kubota, Y., & Kitagawa, S. (2023). Integrated Soft Porosity and Electrical Properties of Conductive-on-Insulating Metal-Organic Framework Nanocrystals. Angewandte Chemie - International Edition, 62(35), Article e202303903. https://doi.org/10.1002/anie.202303903

@article{d1666997816244f99701d8cd1cfdd822,

title = "Integrated Soft Porosity and Electrical Properties of Conductive-on-Insulating Metal-Organic Framework Nanocrystals",

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.",

keywords = "Conductivity, Metal–Organic Frameworks, Operando, Shape Memory, Soft Porosity",

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

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: {\textcopyright} 2023 Wiley-VCH GmbH.",

year = "2023",

month = aug,

day = "28",

doi = "10.1002/anie.202303903",

language = "English (US)",

volume = "62",

journal = "Angewandte Chemie - International Edition",

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publisher = "Wiley",

number = "35",

}

Yao, MS, Otake, KI, Zheng, J, Tsujimoto, M, Gu, YF, Zheng, L, Wang, P, Mohana, S, Bonneau, M, Koganezawa, T, Honma, T, Ashitani, H, Kawaguchi, S, Kubota, Y & Kitagawa, S 2023, 'Integrated Soft Porosity and Electrical Properties of Conductive-on-Insulating Metal-Organic Framework Nanocrystals', Angewandte Chemie - International Edition, vol. 62, no. 35, e202303903. https://doi.org/10.1002/anie.202303903

TY - JOUR

T1 - Integrated Soft Porosity and Electrical Properties of Conductive-on-Insulating Metal-Organic Framework Nanocrystals

AU - Yao, Ming Shui

AU - Otake, Ken ichi

AU - Zheng, Jiajia

AU - Tsujimoto, Masahiko

AU - Gu, Yi Fan

AU - Zheng, Lu

AU - Wang, Ping

AU - Mohana, Shivanna

AU - Bonneau, Mickaele

AU - Koganezawa, Tomoyuki

AU - Honma, Tetsuo

AU - Ashitani, Hirotaka

AU - Kawaguchi, Shogo

AU - Kubota, Yoshiki

AU - Kitagawa, Susumu

N1 - 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.

PY - 2023/8/28

Y1 - 2023/8/28

N2 - 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.

AB - 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.

KW - Conductivity

KW - Metal–Organic Frameworks

KW - Operando

KW - Shape Memory

KW - Soft Porosity

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U2 - 10.1002/anie.202303903

DO - 10.1002/anie.202303903

M3 - Article

C2 - 37211927

AN - SCOPUS:85161452992

SN - 1433-7851

VL - 62

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 35

M1 - e202303903

ER -

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

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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