Boron-imidazolate coordination networks with 3d transition metals for enhanced CO<sub>2</sub> adsorption capability

Kato, Takeshi; Akiyama, Ikuho; Mori, Fumika; Shinohara, Ayumu; Ogura, Yudai; Ito, Akitaka; Ohtani, Masataka

doi:10.1039/d3ma00996c

Cited by 2 publications

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“…This study focused on boron imidazolate frameworks (BIFs), which comprise boron-bridged imidazolate ligands, where four molecules of imidazolate are bound to each boron. BIFs can form a crystal structure similar to zeolites owing to the structural features of the boron-bridged imidazolate ligands. − We proposed that introducing Zn 2+ and B(bim) 4 – would enable the construction of a structure where some of ZIF-7 is replaced by boron. This boron-doping of ZIF-7 is expected to change its gate-opening CO 2 adsorption behavior according to the rotation of the bim ligands.…”

Section: Introductionmentioning

confidence: 99%

Effect of Boron-Doping on Gate-Opening CO₂ Adsorption in Zinc-Benzimidazolate Coordination Networks

Akiyama,

Kato,

Kannaka

et al. 2024

ACS Appl. Mater. Interfaces

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Flexible metal−organic frameworks (MOFs) have attracted much attention as selective gas adsorption and storage. This report describes boron doping in zeolitic imidazolate framework-7 (B-ZIF-7), which exhibits reversible phase transition during CO 2 adsorption/ desorption. We have successfully prepared B-ZIF-7 coordination networks using boron-bridged benzimidazolate (B(bim) 4 − ) as organic ligands. Powder X-ray diffraction (PXRD) measurements and infrared spectroscopy revealed that B-ZIF-7 has a crystal structure similar to that of ZIF-7 while containing boron bridging in the coordination network. Since B-ZIF-7 forms a cationic coordination network, the guest anions are encapsulated within the pore. CO 2 adsorption/ desorption measurements at 300 K showed that B-ZIF-7(NO 3 ), which contains nitrate ions (NO 3 − ) as guest anions in its pores, exhibits a S-shaped CO 2 adsorption/desorption isotherm, which is characteristic of gate-opening type MOFs. Compared with ZIF-7, B-ZIF-7(NO 3 ) has superior CO 2 adsorption capacity in the low-pressure and superior CO 2 storage capacity. The CO 2 adsorption and desorption behavior of B-ZIF-7(NO 3 ) was analyzed by in situ temperature-controlled PXRD measurements and thermogravimetric analysis under a CO 2 atmosphere, and a reversible phase transition was observed. We have also successfully prepared B-ZIF-7(Cl) and B-ZIF-7(OTf) (OTf = CF 3 SO 3 − ) with different guest anions. The CO 2 adsorption/desorption behaviors of B-ZIF-7(Cl) and B-ZIF-7(OTf) were significantly different from those of B-ZIF-7(NO 3 ) and ZIF-7. B-ZIF-7(Cl) showed gate opening at a higher pressure than ZIF-7, and B-ZIF-7(OTf) did not show Sshaped CO 2 adsorption isotherm and showed adsorption behavior in micropores. These results indicate that the CO 2 adsorption behavior of B-ZIF-7 depends on the interaction between the guest anions and CO 2 molecules or the cationic framework and the bulkiness of the guest anions. Boron doping in a coordination network with boron-bridged imidazolate ligands is a promising strategy to increase the gas adsorption capability of porous materials.

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Section: Introductionmentioning

confidence: 99%

Effect of Boron-Doping on Gate-Opening CO₂ Adsorption in Zinc-Benzimidazolate Coordination Networks

Akiyama,

Kato,

Kannaka

et al. 2024

ACS Appl. Mater. Interfaces

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Evolution of the Structure and Morphology of Dual-Linker ZIF-301-eIm

Wei,

Xie,

Wang

et al. 2024

Molecules

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Few studies have reported on the continuous evolution of dual-linker zeolitic imidazolate frameworks’ (ZIFs) structure and morphology during the crystal growth process. Herein, we report the synthesis of a novel ZIF material with CHA topology (ZIF-301-eIm) via the combination of a small-sized 2-ethylimidazole (eIm) with the large-sized 5-chlorobenzimidazole ligand. A series of derivative materials with distinct structures and morphologies were obtained via two pathways: (1) insufficient amount of eIm with prolonged crystallization time (pathway A) and (2) sufficient amount of eIm with prolonged crystallization time (pathway B). Various characterization techniques revealed the continuous evolution of structure and morphology during the crystal growth process. Insufficient amount of eIm and crystallization time (crystallization pathway A) led to ZIF-301-eIm derivatives with defective and open structures alongside an aggregated morphology of nanoparticles. Prolonging the crystallization time allowed small-sized eIm ligands to gradually fill into the framework, resulting in the formation of ZIF-301-eIm-A5 characterized by complete but dense structures with a perfect polyhedral morphology. Remarkably, a sufficient amount of eIm during synthesis (crystallization pathway B) formed ZIF-301-eIm-B1 with a similar structure and morphology to ZIF-301-eIm-A5 in just 1 day. ZIF-301-eIm-B3, with intact, dense structures, exhibits superior acetone/butanol separation performance compared to ZIF-301-eIm-A3 due to small pore windows and large cages facilitating selective adsorption of acetone through exclusion separation.

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Boron-imidazolate coordination networks with 3d transition metals for enhanced CO₂ adsorption capability

Abstract: The synthesis conditions of a sodalite (SOD)-topology coordination network with a boron-imidazolate framework (BIF), namely BIF-3-Cu, were systematically investigated to control the crystal growth process. By optimising the reaction time,...

Cited by 2 publications

References 46 publications

Effect of Boron-Doping on Gate-Opening CO₂ Adsorption in Zinc-Benzimidazolate Coordination Networks

Effect of Boron-Doping on Gate-Opening CO₂ Adsorption in Zinc-Benzimidazolate Coordination Networks

Evolution of the Structure and Morphology of Dual-Linker ZIF-301-eIm

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Boron-imidazolate coordination networks with 3d transition metals for enhanced CO2 adsorption capability

Abstract: The synthesis conditions of a sodalite (SOD)-topology coordination network with a boron-imidazolate framework (BIF), namely BIF-3-Cu, were systematically investigated to control the crystal growth process. By optimising the reaction time,...

Cited by 2 publications

References 46 publications

Effect of Boron-Doping on Gate-Opening CO2 Adsorption in Zinc-Benzimidazolate Coordination Networks

Effect of Boron-Doping on Gate-Opening CO2 Adsorption in Zinc-Benzimidazolate Coordination Networks

Evolution of the Structure and Morphology of Dual-Linker ZIF-301-eIm

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Boron-imidazolate coordination networks with 3d transition metals for enhanced CO₂ adsorption capability

Effect of Boron-Doping on Gate-Opening CO₂ Adsorption in Zinc-Benzimidazolate Coordination Networks

Effect of Boron-Doping on Gate-Opening CO₂ Adsorption in Zinc-Benzimidazolate Coordination Networks