Robust Fluorine-Decorated {Yb<sub>4</sub>}-Organic Framework for C<sub>2</sub>H<sub>6</sub> Capture and Efficient Catalytic Performance on CO<sub>2</sub>-Epoxide Cycloaddition

Fluorine-functionalized MOFs have excellent unusual properties such as gas adsorption and separation and catalysis, but the functionalization of existing ligands and the self-assembly of functionalized MOFs remain a challenge. Herein, we report a robust fluorine-functionalized nanochannel-based ytterbium(III)-organic framework of {(Me<sub>2</sub>NH<sub>2</sub>)[Yb<sub>4</sub>(CFPDA)<sub>2</sub>(μ<sub>2</sub>-HCO<sub>2</sub>)(μ<sub>3</sub>-OH)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>]·4DMF·5H<sub>2</sub>O}<sub><i>n</i></sub> (<b>NUC-122</b>, H<sub>5</sub>CFPDA = 4,4'-(4-(4-carboxy-2-fluorophenyl)pyridine-2,6-diyl)diisophthalic acid) with [Yb<sub>4</sub>(μ<sub>3</sub>-OH)<sub>2</sub>(μ<sub>2</sub>-HCO<sub>2</sub>)(H<sub>2</sub>O)<sub>2</sub>] clusters as secondary building units (SBUs). Compared to reported anionic skeleton of [Yb<sub>4</sub>(BDCP)<sub>2</sub>(μ<sub>2</sub>-HCO<sub>2</sub>)(μ<sub>3</sub>-OH)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>]<sub><i>n</i></sub> (<b>NUC-38Yb</b>), the void volume of <b>NUC-122</b> (54.1%) is slightly lower than that of <b>NUC-38Yb</b> (56.7%), which is caused by functionalized fluorine atoms on the ligand of H<sub>5</sub>BDCP. Because of the introduction of fluorine groups, activated <b>NUC-122a</b> displays a higher adsorption capacity for CO<sub>2</sub> along with the value of 117.5 cm<sup>3</sup>/g (273 K) and 63.1 cm<sup>3</sup>/g (298 K). Further, activated <b>NUC-122a</b> has a high ethane (C<sub>2</sub>H<sub>6</sub>) separation performance over the mixture of C<sub>2</sub>H<sub>6</sub>/C<sub>2</sub>H<sub>4</sub> with the selectivity of 1.6, enabling the purity of recycled C<sub>2</sub>H<sub>4</sub> to reach 99.99%. Moreover, the CO<sub>2</sub>-epoxide cycloaddition could be efficiently catalyzed by <b>NUC-122a</b> under comparatively mild conditions. Under optimal catalytic conditions of 0.13 mol % MOFs, 1.69 mol % <i>n</i>-Bu<sub>4</sub>NBr, 0.7 MPa CO<sub>2</sub>, 70 °C, and 3 h, the conversion yield of SO to SC catalyzed by <b>NUC-122a</b> is 26% higher than that catalyzed by <b>NUC-38Yb</b>. The excellent separation and catalytic performance should be attributed to the combined diverse functional groups such as Lewis acidic sites of Yb<sup>3+</sup>, Lewis basic sites of -F and N<sub>pyridine</sub> atoms, and electrophilic H-bond donors (HBD) of μ<sub>3</sub>-OH and μ<sub>2</sub>-HCO<sub>2</sub> moieties. Hence, this work not only reports a fluorine-functionalized multifunctional material but also provides an in-depth insight into the synthetic strategy of functionalized metal-organic host frameworks.

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Publication Details

Journal
ACS Applied Materials & Interfaces
Published
2025-05-08
DOI
https://doi.org/10.1021/acsami.5c07205
Citations
17
Primary Topic
Carbon dioxide utilization in catalysis
Type
article
Field-Weighted Citation Impact
11.98
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article

Robust Fluorine-Decorated {Yb4}-Organic Framework for C2H6 Capture and Efficient Catalytic Performance on CO2-Epoxide Cycloaddition

Fei Yang, Aimiao Qin, Xiutang Zhang, Shu‐Hua Zhang et al.
17 citations
ACS Applied Materials & Interfaces
Carbon dioxide utilization in catalysis
11.98
article

Robust Fluorine-Decorated {Yb4}-Organic Framework for C2H6 Capture and Efficient Catalytic Performance on CO2-Epoxide Cycloaddition

Fei Yang, Aimiao Qin, Xiutang Zhang, Shu‐Hua Zhang, Zhenfeng Wang
article en
17 citations

Abstract

Fluorine-functionalized MOFs have excellent unusual properties such as gas adsorption and separation and catalysis, but the functionalization of existing ligands and the self-assembly of functionalized MOFs remain a challenge. Herein, we report a robust fluorine-functionalized nanochannel-based ytterbium(III)-organic framework of {(Me<sub>2</sub>NH<sub>2</sub>)[Yb<sub>4</sub>(CFPDA)<sub>2</sub>(μ<sub>2</sub>-HCO<sub>2</sub>)(μ<sub>3</sub>-OH)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>]·4DMF·5H<sub>2</sub>O}<sub><i>n</i></sub> (<b>NUC-122</b>, H<sub>5</sub>CFPDA = 4,4'-(4-(4-carboxy-2-fluorophenyl)pyridine-2,6-diyl)diisophthalic acid) with [Yb<sub>4</sub>(μ<sub>3</sub>-OH)<sub>2</sub>(μ<sub>2</sub>-HCO<sub>2</sub>)(H<sub>2</sub>O)<sub>2</sub>] clusters as secondary building units (SBUs). Compared to reported anionic skeleton of [Yb<sub>4</sub>(BDCP)<sub>2</sub>(μ<sub>2</sub>-HCO<sub>2</sub>)(μ<sub>3</sub>-OH)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>]<sub><i>n</i></sub> (<b>NUC-38Yb</b>), the void volume of <b>NUC-122</b> (54.1%) is slightly lower than that of <b>NUC-38Yb</b> (56.7%), which is caused by functionalized fluorine atoms on the ligand of H<sub>5</sub>BDCP. Because of the introduction of fluorine groups, activated <b>NUC-122a</b> displays a higher adsorption capacity for CO<sub>2</sub> along with the value of 117.5 cm<sup>3</sup>/g (273 K) and 63.1 cm<sup>3</sup>/g (298 K). Further, activated <b>NUC-122a</b> has a high ethane (C<sub>2</sub>H<sub>6</sub>) separation performance over the mixture of C<sub>2</sub>H<sub>6</sub>/C<sub>2</sub>H<sub>4</sub> with the selectivity of 1.6, enabling the purity of recycled C<sub>2</sub>H<sub>4</sub> to reach 99.99%. Moreover, the CO<sub>2</sub>-epoxide cycloaddition could be efficiently catalyzed by <b>NUC-122a</b> under comparatively mild conditions. Under optimal catalytic conditions of 0.13 mol % MOFs, 1.69 mol % <i>n</i>-Bu<sub>4</sub>NBr, 0.7 MPa CO<sub>2</sub>, 70 °C, and 3 h, the conversion yield of SO to SC catalyzed by <b>NUC-122a</b> is 26% higher than that catalyzed by <b>NUC-38Yb</b>. The excellent separation and catalytic performance should be attributed to the combined diverse functional groups such as Lewis acidic sites of Yb<sup>3+</sup>, Lewis basic sites of -F and N<sub>pyridine</sub> atoms, and electrophilic H-bond donors (HBD) of μ<sub>3</sub>-OH and μ<sub>2</sub>-HCO<sub>2</sub> moieties. Hence, this work not only reports a fluorine-functionalized multifunctional material but also provides an in-depth insight into the synthetic strategy of functionalized metal-organic host frameworks.

ACS Applied Materials & InterfacesVol. 17(20)
North University of China (CN), Guilin University of Technology (CN), Guangdong University of Petrochemical Technology (CN), Division of Materials Science and Engineering (AU)
Openalex Percentile: Top 1%
Carbon dioxide utilization in catalysis
11.98
DOISourceOpenAlex
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