Mechanical Force Induced Formation of Extrinsic Micropores in Coordination Polymers

Shin-Ichiro Noro; Xin Zheng; AnQi Wang; Kazushige Suzuki; Soracha Kosasang; Satoshi Horike; Daniele Padovan; Kiyotaka Nakajima; Hiroyasu Sato; Kiyonori Takahashi; Takayoshi Nakamura

doi:10.1021/acs.inorgchem.1c02762

Mechanical Force Induced Formation of Extrinsic Micropores in Coordination Polymers

Inorg Chem. 2022 Feb 28;61(8):3379-3386. doi: 10.1021/acs.inorgchem.1c02762. Epub 2022 Feb 16.

Authors

Affiliations

¹ Faculty of Environmental Earth Science, Hokkaido University, Sapporo 060-0810, Japan.
² Graduate School of Environmental Science, Hokkaido University, Sapporo 060-0810, Japan.
³ Department of Chemical and Biomolecular Engineering, School of Energy Science and Engineering, Vidyasirimedhi Institute of Science and Technology, Rayong 21210, Thailand.
⁴ Institute for Integrated Cell-Material Sciences, Institute for Advanced Study, Kyoto University, Kyoto 615-8510, Japan.
⁵ Institute for Catalysis, Hokkaido University, Sapporo 001-0021, Japan.
⁶ Rigaku Corporation, Akishima, Tokyo 196-8666, Japan.
⁷ Research Institute for Electronic Science, Hokkaido University, Sapporo 001-0020, Japan.

PMID: 35172569
DOI: 10.1021/acs.inorgchem.1c02762

Abstract

Mechanical force can be employed not only to efficiently synthesize new materials under environmentally friendly conditions but also to change the macroscopic and microscopic properties of materials. Although coordination polymers (CPs) are attractive functional materials because they possess high structural designability and diversity, mechanical force-induced structural and functional changes of CPs are challenging issues. In this study, two one-dimensional CPs, one a densely packed nonporous CP [Cu₂(bza)₄(pyr)] (1) and the other a porous CP [Cu₂(1-nap)₄(pyr)] (2) (bza = benzoate, 1-nap = 1-naphthoate and pyr = pyrimidine), were subjected to ball-milling to assess the effect of mechanical force on their porosities. Ball mill treatments were found to induce an amorphization and cause a 30 fold enhancement of the CO₂ adsorption amount at 195 K and P/P₀ ∼ 1 for 1 and a slightly decreased CO₂ adsorption amount for 2. The results of thorough characterization studies suggest that the formation of extrinsic micropores in addition to extrinsic mesopores/macropores between particles takes place by ball milling.