eprintid: 10198168
rev_number: 7
eprint_status: archive
userid: 699
dir: disk0/10/19/81/68
datestamp: 2024-10-08 10:54:25
lastmod: 2024-10-08 10:54:25
status_changed: 2024-10-08 10:54:25
type: article
metadata_visibility: show
sword_depositor: 699
creators_name: Chen, L
creators_name: Guan, X
creators_name: Wu, X
creators_name: Asakura, H
creators_name: Hopkinson, DG
creators_name: Allen, C
creators_name: Callison, J
creators_name: Dyson, PJ
creators_name: Wang, FR
title: Thermally stable high-loading single Cu sites on ZSM-5 for selective catalytic oxidation of NH3
ispublished: pub
divisions: UCL
divisions: B04
divisions: F43
keywords: Ammonia oxidation, heterogeneous catalysis, operando spectroscopy, selective catalytic oxidation, single site catalyst
note: Copyright © 2024 the Author(s). Published by PNAS. This
open access article is distributed under Creative Commons
Attribution-NonCommercial-NoDerivatives License 4.0 (CC
BY-NC-ND).
abstract: Rigorous comparisons between single site- and nanoparticle (NP)-dispersed catalysts featuring the same composition, in terms of activity, selectivity, and reaction mechanism, are limited. This limitation is partly due to the tendency of single metal atoms to sinter into aggregated NPs at high loadings and elevated temperatures, driven by a decrease in metal surface free energy. Here, we have developed a unique two-step method for the synthesis of single Cu sites on ZSM-5 (termed CuS/ZSM-5) with high thermal stability. The atomic-level dispersion of single Cu sites was confirmed through scanning transmission electron microscopy, X-ray absorption fine structure (XAFS), and electron paramagnetic resonance spectroscopy. The CuS/ZSM-5 catalyst was compared to a CuO NP-based catalyst (termed CuN/ZSM-5) in the oxidation of NH3 to N2, with the former exhibiting superior activity and selectivity. Furthermore, operando XAFS and diffuse reflectance infrared Fourier transform spectroscopy studies were conducted to simultaneously assess the fate of the Cu and the surface adsorbates, providing a comprehensive understanding of the mechanism of the two catalysts. The study shows that the facile redox behavior exhibited by single Cu sites correlates with the enhanced activity observed for the CuS/ZSM-5 catalyst.
date: 2024-07-23
date_type: published
publisher: Proceedings of the National Academy of Sciences
official_url: https://doi.org/10.1073/pnas.2404830121
oa_status: green
full_text_type: pub
language: eng
primo: open
primo_central: open_green
verified: verified_manual
elements_id: 2299351
doi: 10.1073/pnas.2404830121
medium: Print-Electronic
lyricists_name: Wang, Feng
lyricists_id: FWANG76
actors_name: Wang, Feng
actors_id: FWANG76
actors_role: owner
funding_acknowledgements: EP/X022986/1 [UKRI | Engineering and Physical Sciences Research Council (EPSRC)]; EP/S018204/2 [UKRI | Engineering and Physical Sciences Research Council (EPSRC)]
full_text_status: public
publication: Proceedings of the National Academy of Sciences of the United States of America
volume: 121
number: 31
article_number: e2404830121
event_location: United States
issn: 0027-8424
citation:        Chen, L;    Guan, X;    Wu, X;    Asakura, H;    Hopkinson, DG;    Allen, C;    Callison, J;         ... Wang, FR; + view all <#>        Chen, L;  Guan, X;  Wu, X;  Asakura, H;  Hopkinson, DG;  Allen, C;  Callison, J;  Dyson, PJ;  Wang, FR;   - view fewer <#>    (2024)    Thermally stable high-loading single Cu sites on ZSM-5 for selective catalytic oxidation of NH3.                   Proceedings of the National Academy of Sciences of the United States of America , 121  (31)    , Article e2404830121.  10.1073/pnas.2404830121 <https://doi.org/10.1073/pnas.2404830121>.       Green open access   
 
document_url: https://discovery.ucl.ac.uk/id/eprint/10198168/1/Thermally%20stable%20high-loading%20single%20Cu%20sites%20on%20ZSM-5%20for%20selective%20catalytic%20oxidation%20of%20NHsub3sub.pdf