In Situ Implanting ZrW2 O7 (OH)2 (H2 O)2 Nanorods into Hierarchical Functionalized Metal-Organic Framework via Solvent-Free Approach for Upgrading Catalytic Performance

Gan Ye; Guangming Shi; Hanlu Wang; Xingye Zeng; Lei Wu; Jun Zhou; Qiuli Zhang; Jinshan Wei; Zhiming Li; Long Nie; Jin Wang

doi:10.1002/smll.202311249

In Situ Implanting ZrW₂ O₇ (OH)₂ (H₂ O)₂ Nanorods into Hierarchical Functionalized Metal-Organic Framework via Solvent-Free Approach for Upgrading Catalytic Performance

Small. 2024 Mar 14:e2311249. doi: 10.1002/smll.202311249. Online ahead of print.

Authors

Gan Ye^{1

2}, Guangming Shi¹, Hanlu Wang³, Xingye Zeng⁴, Lei Wu¹, Jun Zhou¹, Qiuli Zhang¹, Jinshan Wei⁵, Zhiming Li⁵, Long Nie⁵, Jin Wang^{2

5}

Affiliations

¹ School of Chemistry and Chemical Engineering, Xi'an University of Architecture and Technology, Xi'an, 710055, China.
² College of Chemistry and Materials Science, Anhui Normal University, Wuhu, 241002, China.
³ College of Chemistry, Guangdong University of Petrochemical Technology, Maoming, 525000, China.
⁴ College of Chemical Engineering, Guangdong University of Petrochemical Technology, Maoming, 525000, China.
⁵ College of Materials Science and Engineering, Shenzhen University, Shenzhen, 518060, China.

PMID: 38482932
DOI: 10.1002/smll.202311249

Abstract

Host-guest catalyst provides new opportunities for targeted applications and the development of new strategies for preparing host-guest catalysts is highly desired. Herein, an in situ solvent-free approach is developed for implanting ZrW₂ O₇ (OH)₂ (H₂ O)₂ nanorods (ZrW-NR) in nitro-functionalized UiO-66(Zr) (UiO-66(Zr)-NO₂ ) with hierarchical porosity, and the encapsulation of ZrW-NR enables the as-prepared host-guest catalyst remarkably enhanced catalytic performance for both for oxidative desulfurization (ODS) and acetalization reactions. ZrW-NR@UiO-66(Zr)-NO₂ can eliminate 500 ppm sulfur within 9 min at 40 °C in ODS, and can transform 5.6 mmol benzaldehyde after 3 min at room temperature in acetalization reaction. Its turnover frequencies reach 72.3 h^-1 at 40 °C for ODS which is 33.4 times higher than UiO-66(Zr)-NO₂ , and 28140 h^-1 for acetalization which is the highest among previous reports. Density functional theory calculation result indicates that the W sites in ZrW-NR can decompose H₂ O₂ to W^VI -peroxo intermediates that contribute to catalytic activity for the ODS reaction. This work opens a new solvent-free approach for preparing MOFs-based host-guest catalysts to upgrade their redox and acid performance.

Keywords: UiO-66(Zr); acetalization; host-guest catalysts; oxidation desulfurization; solvent-free approach.

Abstract

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