Cardiff University | Prifysgol Caerdydd ORCA
Online Research @ Cardiff 
WelshClear Cookie - decide language by browser settings

Direct observation of ammonia storage in UiO-66 incorporating Cu(II) binding sites

Ma, Yujie, Lu, Wanpeng, Han, Xue, Chen, Yinlin, da Silva, Ivan, Lee, Daniel, Sheveleva, Alena M., Wang, Zi, Li, Jiangnan, Li, Weiyao, Fan, Mengtian, Xu, Shaojun, Tuna, Floriana, McInnes, Eric J. L., Cheng, Yongqiang, Rudi?, Svemir, Manuel, Pascal, Frogley, Mark D., Ramirez-Cuesta, Anibal J., Schröder, Martin and Yang, Sihai 2022. Direct observation of ammonia storage in UiO-66 incorporating Cu(II) binding sites. Journal of the American Chemical Society 144 (19) , pp. 8624-8632. 10.1021/jacs.2c00952

[thumbnail of jacs.2c00952.pdf]
Preview
PDF - Published Version
Available under License Creative Commons Attribution.

Download (4MB) | Preview

Abstract

The presence of active sites in metal–organic framework (MOF) materials can control and affect their performance significantly in adsorption and catalysis. However, revealing the interactions between the substrate and active sites in MOFs at atomic precision remains a challenging task. Here, we report the direct observation of binding of NH3 in a series of UiO-66 materials containing atomically dispersed defects and open Cu(I) and Cu(II) sites. While all MOFs in this series exhibit similar surface areas (1111–1135 m2 g–1), decoration of the −OH site in UiO-66-defect with Cu(II) results in a 43% enhancement of the isothermal uptake of NH3 at 273 K and 1.0 bar from 11.8 in UiO-66-defect to 16.9 mmol g–1 in UiO-66-CuII. A 100% enhancement of dynamic adsorption of NH3 at a concentration level of 630 ppm from 2.07 mmol g–1 in UiO-66-defect to 4.15 mmol g–1 in UiO-66-CuII at 298 K is observed. In situ neutron powder diffraction, inelastic neutron scattering, and electron paramagnetic resonance, solid-state nuclear magnetic resonance, and infrared spectroscopies, coupled with modeling reveal that the enhanced NH3 uptake in UiO-66-CuII originates from a {Cu(II)···NH3} interaction, with a reversible change in geometry at Cu(II) from near-linear to trigonal coordination. This work represents the first example of structural elucidation of NH3 binding in MOFs containing open metal sites and will inform the design of new efficient MOF sorbents by targeted control of active sites for NH3 capture and storage.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Cardiff Catalysis Institute (CCI)
Additional Information: Attribution 4.0 International (CC BY 4.0)
Publisher: American Chemical Society
ISSN: 0002-7863
Funders: EPSRC
Date of First Compliant Deposit: 1 July 2022
Date of Acceptance: 9 May 2022
Last Modified: 03 May 2023 15:20
URI: https://orca.cardiff.ac.uk/id/eprint/150961

Citation Data

Cited 26 times in Scopus. View in Scopus. Powered By Scopus® Data

Actions (repository staff only)

Edit Item Edit Item

Downloads

Downloads per month over past year

View more statistics